EP2996172A2 - Biocompatibilité des éléments énergétiques biomédicaux - Google Patents

Biocompatibilité des éléments énergétiques biomédicaux Download PDF

Info

Publication number
EP2996172A2
EP2996172A2 EP15181799.6A EP15181799A EP2996172A2 EP 2996172 A2 EP2996172 A2 EP 2996172A2 EP 15181799 A EP15181799 A EP 15181799A EP 2996172 A2 EP2996172 A2 EP 2996172A2
Authority
EP
European Patent Office
Prior art keywords
battery
layer
cathode
examples
laminar structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15181799.6A
Other languages
German (de)
English (en)
Other versions
EP2996172A3 (fr
Inventor
Frederick A. Flitsch
Daniel B. Otts
Randall B. Pugh
James Daniel Riall
Adam Toner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson and Johnson Vision Care Inc
Original Assignee
Johnson and Johnson Vision Care Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson and Johnson Vision Care Inc filed Critical Johnson and Johnson Vision Care Inc
Publication of EP2996172A2 publication Critical patent/EP2996172A2/fr
Publication of EP2996172A3 publication Critical patent/EP2996172A3/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00807—Producing lenses combined with electronics, e.g. chips
    • B29D11/00817—Producing electro-active lenses or lenses with energy receptors, e.g. batteries or antennas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C13/00—Assembling; Repairing; Cleaning
    • G02C13/001—Assembling; Repairing
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/08—Auxiliary lenses; Arrangements for varying focal length
    • G02C7/081—Ophthalmic lenses with variable focal length
    • G02C7/083—Electrooptic lenses
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/184—Sealing members characterised by their shape or structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • a field of use for the biocompatible batteries may include any biocompatible device or product that requires energy.
  • These medical devices may include, for example, implantable pacemakers, electronic pills for monitoring and/or testing a biological function, surgical devices with active components, contact lenses, infusion pumps, and neurostimulators.
  • Added functionality and an increase in performance to many of the aforementioned medical devices have been theorized and developed.
  • many of these devices now require self-contained energization means that are compatible with the size and shape requirements of these devices, as well as the energy requirements of the new energized components.
  • Some medical devices may include electrical components such as semiconductor devices that perform a variety of functions and may be incorporated into many biocompatible and/or implantable devices.
  • electrical components such as semiconductor devices that perform a variety of functions and may be incorporated into many biocompatible and/or implantable devices.
  • semiconductor components require energy and, thus, energization elements should preferably also be included in such biocompatible devices.
  • the topology and relatively small size of the biocompatible devices may create challenging environments for the definition of various functionalities. In many examples, it may be important to provide safe, reliable, compact and cost-effective means to energize the semiconductor components within the biocompatible devices. Therefore, a need exists for biocompatible energization elements formed for implantation within or upon biocompatible devices where the structure of the millimeter- or smaller-sized energization elements provides enhanced function for the energization element while maintaining biocompatibility.
  • One such energization element used to power a device may be a battery.
  • a battery When using a battery in biomedical type applications, it may be important that the battery structure and design accommodate aspects of biocompatibility. Therefore a need exists for novel examples of forming biocompatible batteries for use in biocompatible energization elements.
  • One general aspect includes a biomedical device including an electroactive component, a biocompatible battery, and an encapsulating layer.
  • the biocompatible battery in this aspect includes a laminar structure, where at least a layer of the laminar structure has a volume removed to form a cavity.
  • the encapsulating layer may comprise hydrogel which may encapsulate at least the electroactive component and the biocompatible battery.
  • the encapsulating layer of hydrogel is used to define a skirt of a contact lens, surrounding internal components of an electroactive lens with a biocompatible layer of hydrogel that interacts with the user's eye surface.
  • the nature of the electrolyte solution provides improvements to the biocompatibility of the biomedical device.
  • the composition of the electrolyte solution may have lowered electrolyte concentrations than typical battery compositions.
  • the composition of electrolytes may mimic the biologic environment that the biomedical device occupies, such as the composition of tear fluid in a non-limiting example.
  • the form factor of the battery and the entire biomedical device may be shrunk to very small limits.
  • the battery thickness or the biomedical device total thickness along a dimension may be less than 1 mm.
  • the battery thickness or the biomedical device total thickness along a dimension or along the extents of the device may be less than 500 microns, or may be less than 250 microns.
  • Another general aspect includes a method of improving biocompatibility in a battery including preparing an electrolyte solution; where the electrolyte solution includes a zinc salt at a concentration less than or approximately equal to 10 percent by weight; obtaining a layer of a laminar structure; cutting out a volume from the layer of the laminar structure, where removing the volume from the layer of the laminar structure forms at least a portion of a cavity; and adding the electrolyte solution, a separator, an anode, an anode current collector, a cathode, and a cathode current collector, to form a biocompatible battery.
  • One general aspect includes a method of improving biocompatibility in a battery including preparing an electrolyte solution; where the electrolyte solution includes contact lens packaging solution; obtaining a layer of a laminar structure; cutting out a volume from the layer of the laminar structure, where removing the volume from the layer of the laminar structure forms at least a portion of a cavity; and adding the electrolyte solution, a separator, an anode, an anode current collector, a cathode, and a cathode current collector, to form the laminar structure.
  • Another general aspect includes a method of improving biocompatibility in a contact lens including: preparing an electrolyte solution; where the electrolyte solution includes contact lens packaging solution; obtaining a layer of a laminar structure; cutting out a volume from the layer of the laminar structure, where removing the volume from the layer of the laminar structure forms at least a first portion of a cavity; adding the electrolyte solution, a separator, an anode, an anode current collector, a cathode, and a cathode current collector, to form the laminar structure; forming a seal of a first envelope layer to a second envelope layer, where the first envelope layer and the second envelope layer surround at least a second portion of the laminar structure; connecting the anode current collector to an electroactive device; connecting the cathode current collector to the electroactive device; and encapsulating the laminar structure and electroactive device in a hydrogel to form an ophthalmic device.
  • One general aspect includes a method of improving biocompatibility in a contact lens including preparing an electrolyte solution; obtaining a layer of a laminar structure; cutting out a volume from the layer of the laminar structure, where removing the volume from the layer of the laminar structure forms at least a first portion of a cavity; adding the electrolyte solution, a separator, an anode, an anode current collector, a cathode, and a cathode current collector, to form the laminar structure; forming a seal of a first envelope layer to a second envelope layer, where the first envelope layer and the second envelope layer surround at least a second portion of the laminar structure; connecting the anode current collector to an electroactive device; connecting the cathode current collector to the electroactive device; and encapsulating the laminar structure and electroactive device in a hydrogel to form an ophthalmic device.
  • the biocompatible battery further includes a sealed encapsulation of the laminar structure where the sealed encapsulation improves the biocompatibility of the biomedical device by decreasing an effusion of the electrolyte to an external environment.
  • the biomedical device may include a sealed encapsulation of the laminar structure, where the sealed encapsulation improves the biocompatibility of the biomedical device by decreasing an effusion of water into an internal environment of the biocompatible battery.
  • a particular class of energization elements may be batteries that are fabricated in layers. The layers may also be classified as laminate layers. A battery formed in this manner may be classified as a laminar battery.
  • FIG. 1A An example of a biomedical device that may incorporate the Energization Elements, batteries, of the present invention may be an electroactive focal-adjusting contact lens.
  • a contact lens insert may be depicted as contact lens insert 100.
  • an electroactive element 120 that may accommodate focal characteristic changes in response to controlling voltages.
  • a circuit 105 to provide those controlling voltage signals as well as to provide other functions such as controlling sensing of the environment for external control signals, may be powered by a biocompatible battery element 110.
  • the battery element 110 may be found as multiple major pieces, in this case three pieces, and may include the various configurations of battery chemistry elements as discussed herein.
  • the battery elements 110 may have various interconnect features to join together pieces as may be depicted underlying the region of interconnect 114.
  • the battery elements 110 may be connected to a circuit element that may have its own substrate 111 upon which interconnect features 125 may be located.
  • the circuit 105 which may be in the form of an integrated circuit, may be electrically and physically connected to the substrate 111 and its interconnect features 125.
  • a cross sectional relief of a contact lens 150 may comprise contact lens insert 100 and its discussed constituents.
  • the contact lens insert 100 may be encapsulated into a skirt of contact lens hydrogel 155 which may encapsulate the contact lens insert 100 and provide a comfortable interface of the contact lens 150 to a user's eye.
  • the battery elements may be formed in a two-dimensional form as depicted in Fig. 1C .
  • the battery elements which are depicted in flat form in Fig. 1C , may connect to a circuit element 163, which in the example of Fig. 1C may comprise two major circuit areas 167.
  • the circuit element 163 may connect to the battery element at an electrical contact 161 and a physical contact 162.
  • the flat structure may be folded into a three-dimensional conical structure as has been described with respect to the present invention.
  • a second electrical contact 166 and a second physical contact 164 may be used to connect and physically stabilize the three-dimensional structure.
  • a representation of this three-dimensional conical structure 180 may be found.
  • the physical and electrical contact points 181 may also be found and the illustration may be viewed as a three-dimensional view of the resulting structure.
  • This structure may include the modular electrical and battery component that will be incorporated with a lens insert into a biocompatible device.
  • the segmented components may be relatively circular-shaped 271, square-shaped 272 or rectangular-shaped.
  • the rectangles may be small rectangular shapes 273, larger rectangular shapes 274, or even larger rectangular shapes 275.
  • the batteries may be formed as flat elements.
  • a rectangular outline 310 of the battery element may be depicted with an anode connection 311 and a cathode connection 312.
  • a circular outline 330 of a battery element may be depicted with an anode connection 331 and a cathode connection 332.
  • the outlines of the battery form may be dimensionally and geometrically configured to fit in custom products.
  • custom "free-form” or “free shape” outlines may be formed which may allow the battery configuration to be optimized to fit within a given product.
  • a "free-form" example of a flat outline may be arcuate in form.
  • the free form may be of such geometry that when formed to a three-dimensional shape, it may take the form of a conical, annular skirt that fits within the constraining confines of a contact lens. It may be clear that similar beneficial geometries may be formed where medical devices have restrictive 2D or 3D shape requirements.
  • Another area for design considerations may relate to electrical requirements of the device, which may be provided by the battery.
  • an appropriate battery may need to meet the full electrical requirements of the system when operating in a non-connected or non-externally powered mode.
  • An emerging field of non-connected or non-externally powered biomedical devices may include, for example, vision-correcting contact lenses, health monitoring devices, pill cameras, and novelty devices.
  • Recent developments in integrated circuit (IC) technology may permit meaningful electrical operation at very low current levels, for example, picoamps of standby current and microamps of operating current. IC's may also permit very small devices.
  • Microbatteries for biomedical applications may be required to meet many simultaneous, challenging requirements.
  • the microbattery may be required to have the capability to deliver a suitable operating voltage to an incorporated electrical circuit.
  • This operating voltage may be influenced by several factors including the IC process "node,” the output voltage from the circuit to another device, and a particular current consumption target which may also relate to a desired device lifetime.
  • nodes may typically be differentiated by the minimum feature size of a transistor, such as its "so-called" transistor channel.
  • This physical feature along with other parameters of the IC fabrication, such as gate oxide thickness, may be associated with a resulting rating standard for "turn-on” or “threshold” voltages of field-effect transistors (FET's) fabricated in the given process node.
  • FET's field-effect transistors
  • it may be common to find FET's with turn-on voltages of 5.0V.
  • the FET's may turn-on at 1.2, 1.8, and 2.5V.
  • the IC foundry may supply standard cells of digital blocks, for example, inverters and flip-flops that have been characterized and are rated for use over certain voltage ranges.
  • Designers chose an IC process node based on several factors including density of digital devices, analog/digital mixed signal devices, leakage current, wiring layers, and availability of specialty devices such as high-voltage FET's. Given these parametric aspects of the electrical components, which may draw power from a microbattery, it may be important for the microbattery power source to be matched to the requirements of the chosen process node and IC design, especially in terms of available voltage and current.
  • an electrical circuit powered by a microbattery may connect to another device.
  • the microbattery-powered electrical circuit may connect to an actuator or a transducer.
  • these may include a light-emitting diode (LED), a sensor, a microelectromechanical system (MEMS) pump, or numerous other such devices.
  • LED light-emitting diode
  • MEMS microelectromechanical system
  • such connected devices may require higher operating voltage conditions than common IC process nodes. For example, a variable-focus lens may require 35V to activate. The operating voltage provided by the battery may therefore be a critical consideration when designing such a system.
  • the efficiency of a lens driver to produce 35V from a 1V battery may be significantly less than it might be when operating from a 2V battery. Further requirements, such as die size, may be dramatically different considering the operating parameters of the microbattery as well.
  • the open-circuit voltage is the potential produced by the battery cell with infinite load resistance.
  • the loaded voltage is the potential produced by the cell with an appropriate, and typically also specified, load impedance placed across the cell terminals.
  • the cutoff voltage is typically a voltage at which most of the battery has been discharged.
  • the cutoff voltage may represent a voltage, or degree of discharge, below which the battery should not be discharged to avoid deleterious effects such as excessive gassing.
  • the cutoff voltage may typically be influenced by the circuit to which the battery is connected, not just the battery itself, for example, the minimum operating voltage of the electronic circuit.
  • an alkaline cell may have an open-circuit voltage of 1.6V, a loaded voltage in the range 1.0 to 1.5V, and a cutoff voltage of 1.0V.
  • the voltage of a given microbattery cell design may depend upon other factors of the cell chemistry employed. And, different cell chemistry may therefore have different cell voltages.
  • Cells may be connected in series to increase voltage; however, this combination may come with tradeoffs to size, internal resistance, and battery complexity. Cells may also be combined in parallel configurations to decrease resistance and increase capacity; however, such a combination may tradeoff size and shelf life.
  • Battery capacity may be the ability of a battery to deliver current, or do work, for a period of time. Battery capacity may typically be specified in units such as microamp-hours. A battery that may deliver 1 microamp of current for 1 hour has 1 microamp-hour of capacity. Capacity may typically be increased by increasing the mass (and hence volume) of reactants within a battery device; however, it may be appreciated that biomedical devices may be significantly constrained on available volume. Battery capacity may also be influenced by electrode and electrolyte material.
  • a battery may be required to source current over a range of values.
  • a leakage current on the order of picoamps to nanoamps may flow through circuits, interconnects, and insulators.
  • circuitry may consume quiescent current to sample sensors, run timers, and perform such low power consumption functions.
  • Quiescent current consumption may be on the order of nanoamps to milliamps.
  • Circuitry may also have even higher peak current demands, for example, when writing flash memory or communicating over radio frequency (RF). This peak current may extend to tens of milliamps or more.
  • RF radio frequency
  • Shelf life typically refers to the period of time which a battery may survive in storage and still maintain useful operating parameters. Shelf life may be particularly important for biomedical devices for several reasons. Electronic devices may displace non-powered devices, as for example may be the case for the introduction of an electronic contact lens. Products in these existing market spaces may have established shelf life requirements, for example, three years, due to customer, supply chain, and other requirements. It may typically be desired that such specifications not be altered for new products. Shelf life requirements may also be set by the distribution, inventory, and use methods of a device including a microbattery. Accordingly, microbatteries for biomedical devices may have specific shelf life requirements, which may be, for example, measured in the number of years.
  • three-dimensional biocompatible energization elements may be rechargeable.
  • an inductive coil may also be fabricated on the three-dimensional surface. The inductive coil could then be energized with a radio-frequency ("RF") fob.
  • the inductive coil may be connected to the three-dimensional biocompatible energization element to recharge the energization element when RF is applied to the inductive coil.
  • photovoltaics may also be fabricated on the three-dimensional surface and connected to the three-dimensional biocompatible energization element. When exposed to light or photons, the photovoltaics will produce electrons to recharge the energization element.
  • a battery may function to provide the electrical energy for an electrical system.
  • the battery may be electrically connected to the circuit of the electrical system.
  • the connections between a circuit and a battery may be classified as interconnects. These interconnects may become increasingly challenging for biomedical microbatteries due to several factors.
  • powered biomedical devices may be very small thus allowing little area and volume for the interconnects. The restrictions of size and area may impact the electrical resistance and reliability of the interconnections.
  • a battery may contain a liquid electrolyte which could boil at high temperature. This restriction may directly compete with the desire to use a solder interconnect which may, for example, require relatively high temperatures such as 250 degrees Celsius to melt.
  • the battery chemistry, including the electrolyte, and the heat source used to form solder based interconnects may be isolated spatially from each other. In the cases of emerging biomedical devices, the small size may preclude the separation of electrolyte and solder joints by sufficient distance to reduce heat conduction.
  • Interconnects may allow current to flow to and from the battery in connection with an external circuit. Such interconnects may interface with the environments inside and outside the battery, and may cross the boundary or seal between those environments. These interconnects may be considered as traces, making connections to an external circuit, passing through the battery seal, and then connecting to the current collectors inside the battery. As such, these interconnects may have several requirements. Outside the battery, the interconnects may resemble typical printed circuit traces. They may be soldered to, or otherwise connect to, other traces. In an example where the battery is a separate physical element from a circuit board compriseing an integrated circuit, the battery interconnect may allow for connection to the external circuit. This connection may be formed with solder, conductive tape, conductive ink or epoxy, or other means. The interconnect traces may need to survive in the environment outside the battery, for example, not corroding in the presence of oxygen.
  • Adhesion may be required between the seal and interconnect in addition to the adhesion which may be required between the seal and battery package.
  • Seal integrity may need to be maintained in the presence of electrolyte and other materials inside the battery.
  • Interconnects which may typically be metallic, may be known as points of failure in battery packaging. The electrical potential and/or flow of current may increase the tendency for electrolyte to "creep" along the interconnect. Accordingly, an interconnect may need to be engineered to maintain seal integrity.
  • the interconnects may interface with the current collectors or may actually form the current collectors.
  • the interconnect may need to meet the requirements of the current collectors as described herein, or may need to form an electrical connection to such current collectors.
  • metal foils are available in thickness of 25 microns or less, which make them suitable for very thin batteries. Such foil may also be sourced with low surface roughness and contamination, two factors which may be critical for battery performance.
  • the foils may include zinc, nickel, brass, copper, titanium, other metals, and various alloys.
  • a modular battery component may be formed according to some aspects and examples of the present invention.
  • the modular battery assembly may be a separate component from other parts of the biomedical device.
  • such a design may include a modular battery that is separate from the rest of a media insert.
  • a modular battery component may be formed in a separate, non-integrated process which may alleviate the need to handle rigid, three-dimensionally formed optical plastic components.
  • the sources of manufacturing may be more flexible and may operate in a more parallel mode to the manufacturing of the other components in the biomedical device.
  • the fabrication of the modular battery components may be decoupled from the characteristics of three-dimensional (3D) shaped devices.
  • 3D three-dimensional
  • a modular battery system may be fabricated in a flat or roughly two-dimensional (2D) perspective and then shaped to the appropriate three-dimensional shape.
  • a modular battery component may be tested independently of the rest of the biomedical device and yield loss due to battery components may be sorted before assembly.
  • the resulting modular battery component may be utilized in various media insert constructs that do not have an appropriate rigid region upon which the battery components may be formed; and, in a still further example, the use of modular battery components may facilitate the use of different options for fabrication technologies than might otherwise be utilized, such as, web-based technology (roll to roll), sheet-based technology (sheet-to-sheet), printing, lithography, and "squeegee" processing.
  • the discrete containment aspect of such a device may result in additional material being added to the overall biomedical device construct. Such effects may set a constraint for the use of modular battery solutions when the available space parameters require minimized thickness or volume of solutions.
  • Battery shape requirements may be driven at least in part by the application for which the battery is to be used.
  • Traditional battery form factors may be cylindrical forms or rectangular prisms, made of metal, and may be geared toward products which require large amounts of power for long durations. These applications may be large enough that they may comprise large form factor batteries.
  • planar (2D) solid-state batteries are thin rectangular prisms, typically formed upon inflexible silicon or glass. These planar solid-state batteries may be formed in some examples using silicon wafer-processing technologies.
  • low power, flexible batteries may be formed in a pouch construct, using thin foils or plastic to contain the battery chemistry. These batteries may be made flat (2D), and may be designed to function when bowed to a modest out-of-plane (3D) curvature.
  • the form factor may require a three-dimensional curvature of the battery component where a radius of that curvature may be on the order of approximately 8.4 mm.
  • the nature of such a curvature may be considered to be relatively steep and for reference may approximate the type of curvature found on a human fingertip.
  • the nature of a relative steep curvature creates challenging aspects for manufacture.
  • a modular battery component may be designed such that it may be fabricated in a flat, two-dimensional manner and then formed into a three-dimensional form of relative high curvature.
  • the thickness of the battery component may be an important and limiting parameter.
  • battery thickness may be determined by the combined thicknesses of top and bottom sheets, spacer sheets, and adhesive layer thicknesses. Practical manufacturing aspects may drive certain parameters of film thickness to standard values in available sheet stock.
  • the films may have minimum thickness values to which they may be specified base upon technical considerations relating to chemical compatibility, moisture / gas impermeability, surface finish, and compatibility with coatings that may be deposited upon the film layers.
  • a desired or goal thickness of a finished battery component may be a component thickness that is less than 220 ⁇ m.
  • this desired thickness may be driven by the three-dimensional geometry of an exemplary ophthalmic lens device where the battery component may need to be fit inside the available volume defined by a hydrogel lens shape given end user comfort, biocompatibility, and acceptance constraints.
  • This volume and its effect on the needs of battery component thickness may be a function of total device thickness specification as well as device specification relating to its width, cone angle, and inner diameter.
  • Another important design consideration for the resulting battery component design may relate to the volume available for active battery chemicals and materials in a given battery component design with respect to the resulting chemical energy that may result from that design. This resulting chemical energy may then be balanced for the electrical requirements of a functional biomedical device for its targeted life and operating conditions
  • a flexible battery module may facilitate the previously mentioned ability to fabricate the battery form in a two-dimensional (2D) flat form.
  • the flexibility of the form may allow the two-dimensional battery to then be formed into an appropriate 3D shape to fit into a biomedical device such as a contact lens.
  • a contact lens form of a biomedical device may have advantages for insertion/removal of the media insert based contact lens that may be closer to the insertion/removal of a standard, non-filled hydrogel contact lens.
  • the number of flexures may be important to the engineering of the battery. For example, a battery which may only flex one time from a planar form into a shape suitable for a contact lens may have significantly different design from a battery capable of multiple flexures.
  • the flexure of the battery may also extend beyond the ability to mechanically survive the flexure event.
  • an electrode may be physically capable of flexing without breaking, but the mechanical and electrochemical properties of the electrode may be altered by flexure. Flex-induced changes may appear instantly, for example, as changes to impedance, or flexure may introduce changes which are only apparent in long-term shelf life testing.
  • the battery width requirement may be largely a function of the application in which it is applied.
  • a contact lens battery system may have constrained needs for the specification on the width of a modular battery component.
  • the variable optic portion of the device may occupy a central spherical region of about 7.0 mm in diameter.
  • the exemplary battery elements may be considered as a three-dimensional object, which fits as an annular, conical skirt around the central optic and formed into a truncated conical ring.
  • the required maximum diameter of the rigid insert is a diameter of 8.50 mm, and tangency to a certain diameter sphere may be targeted (as for example in a roughly 8.40 mm diameter), then geometry may dictate what the allowable battery width may be.
  • geometric models that may be useful for calculating desirable specifications for the resulting geometry which in some examples may be termed a conical frustum flattened into a sector of an annulus.
  • Flattened battery width may be driven by two features of the battery element, the active battery components and seal width.
  • a target thickness may be between 0.100 mm and 0.500 mm per side, and the active battery components may be targeted at approximately 0.800 mm wide.
  • Other biomedical devices may have differing design constraints but the principles for flexible flat battery elements may apply in similar fashion.
  • battery elements may be designed in manners that segment the regions of active battery chemistry. There may be numerous advantages from the division of the active battery components into discrete segments. In a non-limiting example, the fabrication of discrete and smaller elements may facilitate production of the elements. The function of battery elements including numerous smaller elements may be improved. Defects of various kinds may be segmented and non-functional elements may be isolated in some cases to result in decreased loss of function. This may be relevant in examples where the loss of battery electrolyte may occur.
  • the isolation of individualized components may allow for a defect that results in leakage of electrolyte out of the critical regions of the battery to limit the loss of function to that small segment of the total battery element whereas the electrolyte loss through the defect could empty a significantly larger region for batteries configured as a single cell.
  • Smaller cells may result in lowered volume of active battery chemicals on an overall perspective, but the mesh of material surrounding each of the smaller cells may result in a strengthening of the overall structure.
  • the chemical action of the battery involves aqueous chemistry, where water or moisture is an important constituent to control. Therefore it may be important to incorporate sealing mechanisms that retard or prevent the movement of moisture either out of or into the battery body.
  • Moisture barriers may be designed to keep the internal moisture level at a designed level, within some tolerance.
  • a moisture barrier may be divided into two sections or components; namely, the package and the seal.
  • the package may refer to the main material of the enclosure.
  • the package may comprise a bulk material.
  • the Water Vapor Transmission Rate (WVTR) may be an indicator of performance, with ISO, ASTM standards controlling the test procedure, including the environmental conditions operant during the testing. Ideally, the WVTR for a good battery package may be "zero." Exemplary materials with a near-zero WVTR may be glass and metal foils. Plastics, on the other hand, may be inherently porous to moisture, and may vary significantly for different types of plastic. Engineered materials, laminates, or co-extrudes may usually be hybrids of the common package materials.
  • the seal may be the interface between two of the package surfaces.
  • the connecting of seal surfaces finishes the enclosure along with the package.
  • the nature of seal designs may make them difficult to characterize for the seal's WVTR due to difficulty in performing measurements using an ISO or ASTM standard, as the sample size or surface area may not be compatible with those procedures.
  • a practical manner to testing seal integrity may be a functional test of the actual seal design, for some defined conditions.
  • Seal performance may be a function of the seal material, the seal thickness, the seal length, the seal width, and the seal adhesion or intimacy to package substrates.
  • seals may be formed by a welding process that may involve thermal, laser, solvent, friction, ultrasonic, or arc processing.
  • seals may be formed through the use of adhesive sealants such as glues, epoxies, acrylics, natural rubber, and synthetic rubber.
  • adhesive sealants such as glues, epoxies, acrylics, natural rubber, and synthetic rubber.
  • gasket type material may be formed from cork, natural and synthetic rubber, polytetrafluoroethylene (PTFE), polypropylene, and silicones to mention a few non-limiting examples.
  • the batteries according to the present invention may be designed to have a specified operating life.
  • the operating life may be estimated by determining a practical amount of moisture permeability that may be obtained using a particular battery system and then estimating when such a moisture leakage may result in an end of life condition for the battery. For example, if a battery is stored in a wet environment, then the partial pressure difference between inside and outside the battery will be minimal, resulting in a reduced moisture loss rate, and therefore the battery life may be extended.
  • the same exemplary battery stored in a particularly dry and hot environment may have a significantly reduced expectable lifetime due to the strong driving function for moisture loss.
  • Batteries of the type described in the present invention may utilize a separator material that physically and electrically separates the anode and anode current collector portions from the cathode and cathode current collector portions.
  • the separator may be a membrane that is permeable to water and dissolved electrolyte components; however, it may typically be electrically non-conductive. While a myriad of commercially-available separator materials may be known to those of skill in the art, the novel form factor of the present invention may present unique constraints on the task of separator selection, processing, and handling.
  • separators of approximately 25 microns in thickness may be desirable. Some examples which may be advantageous may be about 12 microns in thickness.
  • separators include microfibrillated, microporous polyethylene monolayer and/or polypropylene-polyethylene-polypropylene (PP/PE/PP) trilayer separator membranes such as those produced by Celgard (Charlotte, NC).
  • PP/PE/PP polypropylene-polyethylene-polypropylene
  • a desirable example of separator material may be Celgard M824 PP/PE/PP trilayer membrane having a thickness of 12 microns.
  • separator materials useful for examples of the present invention may include separator membranes including regenerated cellulose (e.g. cellophane).
  • PP/PE/PP trilayer separator membranes may have advantageous thickness and mechanical properties, owing to their polyolefinic character, they may also suffer from a number of disadvantages that may need to be overcome in order to make them useful in examples of the present invention.
  • Roll or sheet stock of PP/PE/PP trilayer separator materials may have numerous wrinkles or other form errors that may be deleterious to the micron-level tolerances applicable to the batteries described herein.
  • polyolefin separators may need to be cut to ultra-precise tolerances for inclusion in the present designs, which may therefore implicate laser cutting as an exemplary method of forming discrete current collectors in desirable shapes with tight tolerances.
  • certain cutting lasers useful for micro fabrication may employ laser wavelengths, e.g. 355 nm, that will not cut polyolefins.
  • the polyolefins do not appreciably absorb the laser energy and are thereby non-ablatable.
  • polyolefin separators may not be inherently wettable to aqueous electrolytes used in the batteries described herein.
  • the membrane may need to be flat and wrinkle-free. If these two conditions are not met, the separator membrane may not be fully cut because the cutting beam may be inhibited as a result of defocusing of or otherwise scattering the incident laser energy. Additionally, if the separator membrane is not flat and wrinkle-free, the form accuracy and geometric tolerances of the separator membrane may not be sufficiently achieved. Allowable tolerances for separators of current examples may be, for example, +0 microns and -20 microns with respect to characteristic lengths and/or radii.
  • Separator stock material may be made flat and wrinkle-free by temporarily laminating the material to a float glass carrier with an appropriate low-volatility liquid.
  • Low-volatility liquids may have advantages over temporary adhesives due to the fragility of the separator membrane and due to the amount of processing time that may be required to release separator membrane from an adhesive layer.
  • achieving a flat and wrinkle-free separator membrane on float glass using a liquid has been observed to be much more facile than using an adhesive.
  • the separator membrane Prior to lamination, the separator membrane may be made free of particulates.
  • float glass substrate may be made to be particulate free by rinsing with an appropriate solvent, ultrasonic cleaning, and/or wiping with clean room wipes.
  • low-volatility liquids may be used for the mechanical purpose of laminating microporous polyolefin separator membranes to a float glass carrier, specific requirements may be imposed on the liquid to facilitate subsequent laser cutting of discrete separator shapes.
  • One requirement may be that the liquid has a surface tension low enough to soak into the pores of the separator material which may easily be verified by visual inspection.
  • the separator material turns from a white color to a translucent appearance when liquid fills the micropores of the material. It may be desirable to choose a liquid that may be benign and "safe" for workers that will be exposed to the preparation and cutting operations of the separator.
  • the liquid may have sufficient solvating power to dissolve advantageous UV absorbers that may facilitate the laser cutting operation.
  • a 12 percent (w/w) solution of avobenzone UV absorber in benzyl benzoate solvent may meet the aforementioned requirements and may lend itself to facilitating the laser cutting of polyolefin separators with high precision and tolerance in short order without an excessive number of passes of the cutting laser beam.
  • separators may be cut with an 8W 355 nm nanosecond diode-pumped solid state laser using this approach where the laser may have settings for low power attenuation (e.g. 3 percent power), a moderate speed of 1 to 10 mm/s, and only 1 to 3 passes of the laser beam. While this UV-absorbing oily composition has been proven to be an effective laminating and cutting process aid, other oily formulations may be envisaged by those of skill in the art and used without limitation.
  • a separator may be cut while fixed to a float glass.
  • One advantage of laser cutting separators while fixed to a float glass carrier may be that a very high number density of separators may be cut from one separator stock sheet much like semiconductor die may be densely arrayed on a silicon wafer. Such an approach may provide economy of scale and parallel processing advantages inherent in semiconductor processes. Furthermore, the generation of scrap separator membrane may be minimized.
  • the oily process aid fluid may be removed by a series of extraction steps with miscible solvents, the last extraction may be performed with a high-volatility solvent such as isopropyl alcohol in some examples.
  • Discrete separators, once extracted, may be stored indefinitely in any suitable low-particle environment.
  • polyolefin separator membranes may be inherently hydrophobic and may need to be made wettable to aqueous surfactants used in the batteries of the present invention.
  • One approach to make the separator membranes wettable may be oxygen plasma treatment. For example, separators may be treated for 1 to 5 minutes in a 100 percent oxygen plasma at a wide variety of power settings and oxygen flow rates. While this approach may improve wettability for a time, it may be well-known that plasma surface modifications provide a transient effect that may not last long enough for robust wetting of electrolyte solutions.
  • Another approach to improve wettability of separator membranes may be to treat the surface by incorporating a suitable surfactant on the membrane. In some cases, the surfactant may be used in conjunction with a hydrophilic polymeric coating that remains within the pores of the separator membrane.
  • Another approach to provide more permanence to the hydrophilicity imparted by an oxidative plasma treatment may be by subsequent treatment with a suitable hydrophilic organosilane.
  • the oxygen plasma may be used to activate and impart functional groups across the entire surface area of the microporous separator.
  • the organosilane may then covalently bond to and/or non-covalently adhere to the plasma treated surface.
  • the inherent porosity of the microporous separator may not be appreciably changed, monolayer surface coverage may also be possible and desired.
  • Prior art methods incorporating surfactants in conjunction with polymeric coatings may require stringent controls over the actual amount of coating applied to the membrane, and may then be subject to process variability.
  • An exemplary organosilane useful in the present invention may be (3-aminopropyl)triethoxysilane.
  • Other hydrophilic organosilanes may be known to those of skill in the art and may be used without limitation.
  • Still another method for making separator membranes wettable by aqueous electrolyte may be the incorporation of a suitable surfactant in the electrolyte formulation.
  • a suitable surfactant for making separator membranes wettable may be the effect that the surfactant may have on the activity of one or more electrodes within the electrochemical cell, for example, by increasing the electrical impedance of the cell.
  • surfactants may have advantageous anti-corrosion properties, specifically in the case of zinc anodes in aqueous electrolytes. Zinc may be an example known to undergo a slow reaction with water to liberate hydrogen gas, which may be undesirable. Numerous surfactants may be known by those of skill in the art to limit rates of said reaction to advantageous levels.
  • the surfactant may so strongly interact with the zinc electrode surface that battery performance may be impeded. Consequently, much care may need to be made in the selection of appropriate surfactant types and loading levels to ensure that separator wettability may be obtained without deleteriously affecting electrochemical performance of the cell.
  • a plurality of surfactants may be used, one being present to impart wettability to the separator membrane and the other being present to facilitate anti-corrosion properties to the zinc anode.
  • no hydrophilic treatment is done to the separator membrane and a surfactant or plurality of surfactants is added to the electrolyte formulation in an amount sufficient to effect wettability of the separator membrane.
  • Discrete separators may be integrated into the laminar microbattery by direct placement into a means for storage including a designed cavity, pocket, or structure within the assembly.
  • this storage means may be formed by a laminar structure having a cutout, which may be a geometric offset of the separator shape, resulting in a cavity, pocket, or structure within the assembly.
  • the storage means may have a ledge or step on which the separator rests during assembly.
  • the ledge or step may optionally include a pressure-sensitive adhesive which retains the discrete separator.
  • the pressure-sensitive adhesive may be the same one used in the construction and stack up of other elements of an exemplary laminar microbattery.
  • the plurality of components comprising the laminar microbatteries of the present invention may be held together with a pressure-sensitive adhesive (PSA) that also serves as a sealant.
  • PSA pressure-sensitive adhesive
  • a myriad of commercially available pressure-sensitive adhesive formulations may exist, such formulations almost always include components that may make them unsuitable for use within a biocompatible laminar microbattery.
  • undesirable components in pressure-sensitive adhesives may include low molecular mass leachable components, antioxidants e.g. BHT and/or MEHQ, plasticizing oils, impurities, oxidatively unstable moieties containing, for example, unsaturated chemical bonds, residual solvents and/or monomers, polymerization initiator fragments, polar tackifiers, and the like.
  • Suitable PSAs may on the other hand exhibit the following properties. They may be able to be applied to laminar components to achieve thin layers on the order of 2 to 20 microns. As well, they may comprise a minimum of, for example, zero undesirable or non-biocompatible components. Additionally, they may have sufficient adhesive and cohesive properties so as to bind the components of the laminar battery together. And, they may be able to flow into the micron-scale features inherent in devices of the present construction while providing for a robust sealing of electrolyte within the battery.
  • the PSAs may have a low permeability to water vapor in order to maintain a desirable aqueous electrolyte composition within the battery even when the battery may be subjected to extremes in humidity for extended periods of time.
  • the PSAs may have good chemical resistance to components of electrolytes such as acids, surfactants, and salts. They may be inert to the effects of water immersion.
  • Suitable PSAs may have a low permeability to oxygen to minimize the rate of direct oxidation, which may be a form of self-discharge, of zinc anodes. And, they may facilitate a finite permeability to hydrogen gas, which may be slowly evolved from zinc anodes in aqueous electrolytes. This property of finite permeability to hydrogen gas may avoid a build-up of internal pressure.
  • polyisobutylene may be a commercially-available material that may be formulated into PSA compositions meeting many if not all desirable requirements. Furthermore, PIB may be an excellent barrier sealant with very low water absorbance and low oxygen permeability.
  • An example of PIB useful in the examples of the present invention may be Oppanol ® B15 by BASF Corporation. Oppanol ® B15 may be dissolved in hydrocarbon solvents such as toluene, heptane, dodecane, mineral spirits, and the like.
  • One exemplary PSA composition may include 30 percent Oppanol ® B15 (w/w) in a solvent mixture, including 70 percent (w/w) toluene and 30 percent dodecane.
  • the adhesive and rheological properties of PIB based PSA's may be determined in some examples by the blending of different molecular mass grades of PIB.
  • a common approach may be to use a majority of low molar mass PIB, e.g. Oppanol ® B10 to effect wetting, tack, and adhesion, and to use a minority of high molar mass PIB to effect toughness and resistance to flow. Consequently, blends of any number of PIB molar mass grades may be envisioned and may be practiced within the scope of the present invention.
  • tackifiers may be added to the PSA formulation so long as the aforementioned requirements may be met.
  • tackifiers impart polar properties to PSA formulations, so they may need to be used with caution so as to not adversely affect the barrier properties of the PSA.
  • tackifiers may in some cases be oxidatively unstable and may include an antioxidant, which could leach out of the PSA.
  • exemplary tackifiers for use in PSA's for biocompatible laminar microbatteries may include fully- or mostly hydrogenated hydrocarbon resin tackifiers such as the Regalrez series of tackifiers from Eastman Chemical Corporation.
  • the packaging may desirably be predominantly foil and/or film based where these packaging layers may be as thin as possible, for example, 10 to 50 microns.
  • the packaging may provide a sufficient diffusion barrier to moisture gain or loss during the shelf life.
  • the packaging may provide a sufficient diffusion barrier to oxygen ingress to limit degradation of zinc anodes by direct oxidation.
  • the packaging may provide a finite permeation pathway to hydrogen gas that may evolve due to direct reduction of water by zinc. And, the packaging may desirably sufficiently contain and may isolate the contents of the battery such that potential exposure to a user may be minimized.
  • packaging constructs may include the following types of functional components: top and bottom packaging layers, PSA layers, spacer layers, interconnect zones, filling ports, and secondary packaging.
  • top and bottom packaging layers may comprise metallic foils or polymer films.
  • Top and bottom packaging layers may comprise multi-layer film constructs containing a plurality of polymer and/or barrier layers. Such film constructs may be referred to as coextruded barrier laminate films.
  • An example of a commercial coextruded barrier laminate film of particular utility in the present invention may be 3M ® Scotchpak 1109 backing which consists of a polyethylene terephthalate (PET) carrier web, a vapor-deposited aluminum barrier layer, and a polyethylene layer including a total average film thickness of 33 microns. Numerous other similar multilayer barrier films may be available and may be used in alternate examples of the present invention.
  • packaging layer surface roughness may be of particular importance because the PSA may also need to seal opposing packaging layer faces.
  • Surface roughness may result from manufacturing processes used in foil and film production, for example, processes employing rolling, extruding, embossing and/or calendaring, among others. If the surface is too rough, PSA may be not able to be applied in a uniform thickness when the desired PSA thickness may be on the order of the surface roughness Ra (the arithmetic average of the roughness profile). Furthermore, PSA's may not adequately seal against an opposing face if the opposing face has roughness that may be on the order of the PSA layer thickness.
  • packaging materials having a surface roughness, Ra, less than 10 microns may be acceptable examples.
  • surface roughness values may be 5 microns or less.
  • the surface roughness may be 1 micron or less.
  • Surface roughness values may be measured by a variety of methods including but not limited to measurement techniques such as white light interferometry, stylus profilometry, and the like. There may be many examples in the art of surface metrology that surface roughness may be described by a number of alternative parameters and that the average surface roughness, Ra, values discussed herein may be meant to be representative of the types of features inherent in the aforementioned manufacturing processes.
  • Figs. 4A - 4N An example of the steps that may be involved in processing biocompatible energization elements may be found referring to Figs. 4A - 4N .
  • the processing at some of the exemplary steps may be found in the individual figures.
  • Fig. 4A a combination of a PET Cathode Spacer 401 and a PET Gap Spacer 404 is illustrated.
  • the PET Cathode Spacer 401 may be formed by applying films of PET 403 which, for example, may be approximately 3 mils thick. On either side of the PET layer may be found PSA layers or these may be capped with a PVDF release layer 402 which may be approximately 1 mil in thickness.
  • the PET Gap spacer 404 may be formed of a PVDF layer 409 which may be approximately 3 mils in thickness.
  • a hole 406 in the PET Gap spacer layer 404 may be cut by laser cutting treatment.
  • the cut PET Gap spacer layer 404 may be laminated 408 to the PET Cathode Spacer layer 401.
  • a cathode spacer hole 410 may be cut by laser cutting treatment. The alignment of this cutting step may be registered to the previously cut features in the PET Gap spacer layer 404.
  • a layer of Celgard 412, for an ultimate separator layer may be bonded to a carrier 411. Proceeding to Fig.
  • the Celgard material may be cut to figures that are between the size of the previous two laser cut holes, and approximately the size of the hole 406 in the PET gap spacer, forming a precut separator 420.
  • a pick and place tool 421 may be used to pick and place discrete pieces of Celgard into their desired locations on the growing device.
  • the placed Celgard pieces 422 are fastened into place and then the PVDF release layer 423 may be removed.
  • the growing device structure may be bonded to a film of the anode 425.
  • the anode 425 may comprise an anode collector film upon which a zinc anode film has been electrodeposited.
  • a cathode slurry 430 may be placed into the formed gap.
  • a squeegee 431 may be used in some examples to spread the cathode mix across a work piece and in the process fill the gaps of the battery devices being formed.
  • the remaining PVDF release layer 432 may be removed which may result in the structure illustrated in Fig. 4K .
  • the entire structure may be subjected to a drying process which may shrink the cathode slurry 440 to also be at the height of the PET layer top.
  • a cathode film layer 450 which may already have the cathode collector film upon it, may be bonded to the growing structure.
  • a laser cutting process may be performed to remove side regions 460 and yield a battery element 470.
  • the cathode chemistry 510 may be located in contact with the cathode and cathode collector 520.
  • a pressure-sensitive adhesive layer 530 may hold and seal the cathode collector 520 to a PET Spacer layer 540.
  • On the other side of the PET Spacer layer 540 may be another PSA layer 550, which seals and adheres the PET Spacer layer 540 to the PET Gap layer 560.
  • Another PSA layer 565 may seal and adhere the PET Gap layer 560 to the anode and anode current collector layers.
  • a zinc plated layer 570 may be plated onto the anode current collector 580.
  • the separator layer 590 may be located within the structure to perform the associated functions as have been defined in the present invention. In some examples, an electrolyte may be added during the processing of the device, in other examples, the separator may already include electrolyte.
  • FIGs. 6A - 6F An example of the steps that may be involved in processing biocompatible energization elements is found in Figs. 6A - 6F .
  • the processing at some of the exemplary steps may be found in the individual figures.
  • the laminar structure may comprise two laminar construct release layers, 602 and 602a; two laminar construct adhesive layers 604 and 604a, located between the laminar construct release layers 602 and 602a; and a laminar construct core 606, located between the two laminar construct adhesive layers 604 and 604a.
  • the laminar construct release layers, 602 and 602a, and adhesive layers, 604 and 604a may be produced or purchased, such as a commercially available pressure-sensitive adhesive transfer tape with primary liner layer.
  • the laminar construct adhesive layers may be a PVDF layer which may be approximately 1-3 millimeters in thickness and cap the laminar construct core 606.
  • the laminar construct core 606 may comprise a thermoplastic polymer resin such as polyethylene terephthalate, which, for example, may be approximately 3 millimeters thick. Proceeding to Fig. 6B , a means for storing the cathode mixture, such as a cavity for the cathode pocket 608, may be cut in the laminar construct by laser cutting treatment.
  • a thermoplastic polymer resin such as polyethylene terephthalate, which, for example, may be approximately 3 millimeters thick.
  • the bottom laminar construct release layer 602a may be removed from the laminar construct, exposing the laminar construct adhesive layer 604a.
  • the laminar construct adhesive layer 604a may then be used to adhere an anode connection foil 610 to cover the bottom opening of the cathode pocket 608.
  • the anode connection foil 610 may be protected on the exposed bottom layer by adhering a masking layer 612.
  • the masking layer 612 may be a commercially available PSA transfer tape with a primary liner.
  • the anode connection foil 610 may be electroplated with a coherent metal 614, zinc, for example, which coats the exposed section of the anode connection foil 610 inside of the cathode pocket. Proceeding to 6F, the anode electrical collection masking layer 612 is removed from the bottom of the anode connection foil 610 after electroplating.
  • Figs. 7A - 7F illustrate an alternate mode of processing the steps illustrated in Figs. 6A - 6F .
  • Figs. 7A - 7B may illustrate similar processes as depicted in Figs. 6A - 6B .
  • the laminar structure may comprise two laminar construct release layers, 702 and 702a, one layer on either end; two laminar construct adhesive layers, 704 and 704a, located between the laminar construct release layers 702 and 702a; and a laminar construct core 706, located between the two laminar construct adhesive layers 704 and 704a.
  • the laminar construct release layers and adhesive layers may be produced or purchased, such as a commercially available pressure-sensitive adhesive transfer tape with primary liner layer.
  • the laminar construct adhesive layers may be a polyvinylidene fluoride (PVDF) layer which may be approximately 1-3 millimeters in thickness and cap the laminar construct core 706.
  • the laminar construct core 706 may comprise a thermoplastic polymer resin such as polyethylene terephthalate, which, for example, may be approximately 3 millimeters thick.
  • a storage means such as a cavity, for the cathode pocket 708, may be cut in the laminar construct by laser cutting treatment.
  • an anode connection foil 710 may be obtained and a protective masking layer 712 applied to one side.
  • the anode connection foil 710 may be electroplated with a layer 714 of a coherent metal, for example, zinc. Proceeding to Fig. 7E , the laminar constructs of Figs. 7B and 7D may be combined to form a new laminar construct as depicted in Fig. 7E by adhering the construct of Fig. 7B to the electroplated layer 714 of Fig. 7D .
  • the release layer 702a of Fig 7B may be removed in order to expose adhesive layer 704a of Fig. 7B for adherence onto electroplated layer 714 of Fig. 7D . Proceeding next to Fig 7F , the anode protective masking layer 712 may be removed from the bottom of the anode connection foil 710.
  • Figs. 8A-8H illustrate exemplary implementations of energization elements to a biocompatible laminar structure, which at times is referred to as a laminar assembly or a laminate assembly herein, similar to, for example, those illustrated in Figs. 6A - 6F and 7A - 7F .
  • a hydrogel separator precursor mixture 820 may be deposited on the surface of the laminate assembly.
  • the hydrogel precursor mixture 820 may be applied up a release layer 802.
  • the hydrogel separator precursor mixture 820 may be squeegeed 850 into the cathode pocket while being cleaned off of the release layer 802.
  • squeegeed may generally refer to the use of a planarizing or scraping tool to rub across the surface and move fluid material over the surface and into cavities as they exist.
  • the process of squeegeeing may be performed by equipment similar to the vernacular "Squeegee” type device or alternatively and planarizing device such as knife edges, razor edges and the like which may be made of numerous materials as may be chemically consistent with the material to be moved.
  • the processing depicted at Fig. 8B may be performed several times to ensure coating of the cathode pocket, and increment the thickness of resulting features.
  • the hydrogel separator precursor mixture may be allowed to dry in order to evaporate materials, which may typically be solvents or diluents of various types, from the hydrogel separator precursor mixture, and then the dispensed and applied materials may be cured. It may be possible to repeat both of the processes depicted at Fig. 8B and Fig. 8C in combination in some examples.
  • the hydrogel separator precursor mixture may be cured by exposure to heat while in other examples the curing may be performed by exposure to photon energy. In still further examples the curing may involve both exposure to photon energy and to heat. There may be numerous manners to cure the hydrogel separator precursor mixture.
  • the result of curing may be to form the hydrogel separator precursor material to the wall of the cavity as well as the surface region in proximity to an anode or cathode feature which in the present example may be an anode feature. Adherence of the material to the sidewalls of the cavity may be useful in the separation function of a separator.
  • the result of curing may be to form an anhydrous polymerized precursor mixture concentrate 822 which may be simply considered the separator of the cell. Proceeding to Fig. 8D , cathode slurry 830 may be deposited onto the surface of the laminar construct release layer 802. Next, at Fig.
  • the cathode slurry 830 may be squeegeed by device 850 into the cathode pocket and onto the anhydrous polymerized precursor mixture concentrate 822.
  • the cathode slurry may be moved to its desired location in the cavity while simultaneously being cleaned off to a large degree from the laminar construct release layer 802.
  • the process of Fig. 8E may be performed several times to ensure coating of the cathode slurry 830 on top of the anhydrous polymerized precursor mixture concentrate 822.
  • the cathode slurry may be allowed to dry down to form an isolated cathode fill 832 on top of the anhydrous polymerized precursor mixture concentrate 822, filling in the remainder of the cathode pocket.
  • an electrolyte formulation 840 may be added on to the isolated cathode fill 832 and allowed to hydrate the isolated cathode fill 832 and the anhydrous polymerized precursor mixture concentrate 822.
  • a cathode connection foil 816 may be adhered to the remaining laminar construct adhesive layer 804 by removing the remaining laminar construct release layer 802 and pressing the connection foil 816 in place. The resulting placement may result in covering the hydrated cathode fill 842 as well as establishing electrical contact to the cathode fill 842 as a cathode current collector and connection means.
  • Figs. 9A through 9C illustrate an alternative example of the resulting laminate assembly from Fig. 7D .
  • the anode connection foil 710 may be obtained and a protective masking layer 712 applied to one side.
  • the anode connection foil 710 may be plated with a layer 714 of coherent metal with, for example, zinc.
  • a hydrogel separator 910 may be applied without the use of the squeegee method illustrated in Fig. 8E .
  • the hydrogel separator precursor mixture may be applied in various manners, for example, a preformed film of the mixture may be adhered by physical adherence; alternatively, a diluted mixture of the hydrogel separator precursor mixture may be dispensed and then adjusted to a desired thickness by the processing of spin coating. Alternatively the material may be applied by spray coating, or any other processing equivalent.
  • Fig. 9C processing is depicted to create a segment of the hydrogel separator that may function as a containment around a separator region. The processing may create a region that limits the flow, or diffusion, of materials such as electrolyte outside the internal structure of the formed battery elements. Such a blocking feature 920 of various types may therefore be formed.
  • the blocking feature 920 may correspond to a highly crosslinked region of the separator layer as may be formed in some examples by increased exposure to photon energy in the desired region of the blocking feature 920.
  • materials may be added to the hydrogel separator material before it is cured to create regionally differentiated portions that upon curing become the blocking feature 920.
  • regions of the hydrogel separator material may be removed either before or after curing by various techniques including, for example, chemical etching of the layer with masking to define the regional extent. The region of removed material may create a blocking feature in its own right or alternatively material may be added back into the void to create a blocking feature.
  • the processing of the impermeable segment may occur through several methods including image out processing, increased crosslinking, heavy photodosing, back-filling, or omission of hydrogel adherence to create a void.
  • a laminate construct or assembly of the type depicted as the result of the processing in Fig. 9C may be formed without the blocking feature 920.
  • a discrete separator may be precluded due to a variety of reasons such as the cost, the availability of materials, the quality of materials, or the complexity of processing for some material options as non-limiting examples.
  • a cast or form-in-place separator which is illustrated in the processes of Figs. 8A - 8H , for example, may provide desirable benefits. While starch or pasted separators have been used commercially with success in AA and other Leclanché format or zinc-carbon batteries, such separators may be unsuitable in some ways for use in certain examples of laminar microbatteries. Particular attention may need to be paid to the uniformity and consistency of geometry for any separator used in the batteries of the present invention. Precise control over separator volume may be needed to facilitate precise subsequent incorporation of known cathode volumes and subsequent realization of consistent discharge capacities and cell performance.
  • a method to achieve a uniform, mechanically robust form-in-place separator may be to use UV-curable hydrogel formulations.
  • Numerous water-permeable hydrogel formulations may be known in various industries, for example, the contact lens industry.
  • An example of a common hydrogel in the contact lens industry may be poly(hydroxyethylmethacrylate) crosslinked gel, or simply pHEMA.
  • pHEMA may possess many attractive properties for use in Leclanche and zinc-carbon batteries. pHEMA typically may maintain a water content of approximately 30-40 percent in the hydrated state while maintaining an elastic modulus of about 100 psi or greater.
  • modulus and water content properties of crosslinked hydrogels may be adjusted by one of ordinary skill in the art by incorporating additional hydrophilic monomeric (e.g. methacrylic acid) or polymeric (e.g. polyvinylpyrrolidone) components.
  • additional hydrophilic monomeric e.g. methacrylic acid
  • polymeric e.g. polyvinylpyrrolidone
  • the water content, or more specifically, the ionic permeability of the hydrogel may be adjusted by formulation.
  • a castable and polymerizable hydrogel formulation may comprise one or more diluents to facilitate processing.
  • the diluent may be chosen to be volatile such that the castable mixture may be squeegeed into a cavity, and then allowed a sufficient drying time to remove the volatile solvent component. After drying, a bulk photopolymerization may be initiated by exposure to actinic radiation of appropriate wavelength, such as blue UV light at 420 nm, for the chosen photoinitiator, such as CGI 819.
  • the volatile diluent may help to provide a desirable application viscosity so as to facilitate casting a uniform layer of polymerizable material in the cavity.
  • the volatile diluent may also provide beneficial surface tension lowering effects, particularly in the case where strongly polar monomers are incorporated in the formulation.
  • Another aspect that may be important to achieve the casting of a uniform layer of polymerizable material in the cavity may be the application viscosity.
  • Common small molar mass reactive monomers typically do not have very high viscosities, which may be typically only a few centipoise.
  • a high molar mass polymeric component known to be compatible with the polymerizable material may be selected for incorporation into the formulation.
  • Examples of high molar mass polymers which may be suitable for incorporation into exemplary formulations may include polyvinylpyrrolidone and polyethylene oxide.
  • the castable, polymerizable separator may be advantageously applied into a designed cavity, as previously described. In alternative examples, there may be no cavity at the time of polymerization. Instead, the castable, polymerizable separator formulation may be coated onto an electrode-containing substrate, for example, patterned zinc plated brass, and then subsequently exposed to actinic radiation using a photomask to selectively polymerize the separator material in targeted areas. Unreacted separator material may then be removed by exposure to appropriate rinsing solvents. In these examples, the separator material may be designated as a photo-patternable separator.
  • the separator may have a number of properties that may be important to its function.
  • the separator may desirably be formed in such a manner as to create a physical barrier such that layers on either side of the separator do not physically contact one another.
  • the layer may therefore have an important characteristic of uniform thickness, since while a thin layer may be desirable for numerous reasons, a void or gap free layer may be essential.
  • the thin layer may desirably have a high permeability to allow for the free flow of ions.
  • the separator requires optimal water uptake to optimize mechanical properties of the separator.
  • the formulation may include a crosslinking component, a hydrophilic polymer component, and a solvent component.
  • a crosslinker may be a monomer with two or more polymerizable double bonds.
  • Suitable crosslinkers may be compounds with two or more polymerizable functional groups.
  • suitable hydrophilic crosslinkers may also include compounds having two or more polymerizable functional groups, as well as hydrophilic functional groups such as polyether, amide or hydroxyl groups. Specific examples may include TEGDMA (tetraethyleneglycol dimethacrylate), TrEGDMA (triethyleneglycol dimethacrylate), ethyleneglycol dimethacylate (EGDMA), ethylenediamine dimethyacrylamide, glycerol dimethacrylate and/or combinations thereof.
  • the amounts of crosslinker that may be used in some examples may range, e.g., from about 0.000415 to about 0.0156 mole per 100 grams of reactive components in the reaction mixture.
  • the amount of hydrophilic crosslinker used may generally be about 0 to about 2 weight percent and, for example, from about 0.5 to about 2 weight percent.
  • Hydrophilic polymer components capable of increasing the viscosity of the reactive mixture and/or increasing the degree of hydrogen bonding with the slow-reacting hydrophilic monomer, such as high molecular weight hydrophilic polymers, may be desirable.
  • the high molecular weight hydrophilic polymers provide improved wettability, and in some examples may improve wettability to the separator of the present invention.
  • high molecular weight hydrophilic polymers may be hydrogen bond receivers which in aqueous environments, hydrogen bond to water, thus becoming effectively more hydrophilic. The absence of water may facilitate the incorporation of the hydrophilic polymer in the reaction mixture.
  • any high molecular weight polymer will be useful in the present invention provided that when the polymer is added to an exemplary silicone hydrogel formulation, the hydrophilic polymer (a) does not substantially phase separate from the reaction mixture and (b) imparts wettability to the resulting cured polymer.
  • the high molecular weight hydrophilic polymer may be soluble in the diluent at processing temperatures. Manufacturing processes which use water or water soluble diluents, such as isopropyl alcohol (IPA), may be desirable examples due to their simplicity and reduced cost. In these examples, high molecular weight hydrophilic polymers which are water soluble at processing temperatures may also be desirable examples.
  • IPA isopropyl alcohol
  • high molecular weight hydrophilic polymers may include but are not limited to polyamides, polylactones, polyimides, polylactams and functionalized polyamides, polylactones, polyimides, polylactams, such as PVP and copolymers thereof, or alternatively, DMA functionalized by copolymerizing DMA with a lesser molar amount of a hydroxyl-functional monomer such as HEMA, and then reacting the hydroxyl groups of the resulting copolymer with materials containing radical polymerizable groups.
  • High molecular weight hydrophilic polymers may include but are not limited to poly-N-vinyl pyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N--N-dimethylacrylamide, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, poly 2 ethyl oxazoline, heparin polysaccharides, polysaccharides, mixtures and copolymers (including block or random, branched, multichain,
  • Additives may include but are not limited to ultra-violet absorbing compounds, photo-initiators such as CGI 819, reactive tints, antimicrobial compounds, pigments, photochromic, release agents, combinations thereof and the like.
  • the method associated with these types of separators may also include receiving CGI 819; then mixing with PVP, HEMA, EGDMA and IPA; and then curing the resulting mixture with a heat source or an exposure to photons.
  • the exposure to photons may occur where the photons' energy is consistent with a wavelength occurring in the ultraviolet portion of the electromagnetic spectrum.
  • Other methods of initiating polymerization generally performed in polymerization reactions are within the scope of the present invention.
  • the cathode current collector may be a sintered carbon rod. This type of material may face technical hurdles for thin electrochemical cells of the present invention.
  • printed carbon inks may be used in thin electrochemical cells to replace a sintered carbon rod for the cathode current collector, and in these examples, the resulting device may be formed without significant impairment to the resulting electrochemical cell.
  • the carbon inks may be applied directly to packaging materials which may comprise polymer films, or in some cases metal foils. In the examples where the packaging film may be a metal foil, the carbon ink may need to protect the underlying metal foil from chemical degradation and/or corrosion by the electrolyte.
  • the carbon ink current collector may need to provide electrical conductivity from the inside of the electrochemical cell to the outside of the electrochemical cell, implying sealing around or through the carbon ink. Due to the porous nature of carbon inks, this may be not easily accomplished without significant challenges. Carbon inks also may be applied in layers that have finite and relatively small thickness, for example, 10 to 20 microns. In a thin electrochemical cell design in which the total internal package thickness may only be about 100 to 150 microns, the thickness of a carbon ink layer may take up a significant fraction of the total internal volume of the electrochemical cell, thereby negatively impacting electrical performance of the cell.
  • the thin nature of the overall battery and the current collector in particular may imply a small cross-sectional area for the current collector.
  • the bulk resistivity of carbon ink may be insufficient to meet the resistance requirement of thin batteries.
  • Inks filled with silver or other conductive metals may also be considered to decrease resistance and/or thickness, but they may introduce new challenges such as incompatibility with novel electrolytes.
  • a thin metal foil as the current collector, or to apply a thin metal film to an underlying polymer packaging layer to act as the current collector.
  • Such metal foils may have significantly lower resistivity, thereby allowing them to meet electrical resistance requirements with much less thickness than printed carbon inks.
  • one or more of the top and/or bottom packaging layers may serve as a substrate for a sputtered current collector metal or metal stack.
  • 3M ® Scotchpak 1109 backing may be metallized using physical vapor deposition (PVD) of one or more metallic layers useful as a current collector for a cathode.
  • Examplary metal stacks useful as cathode current collectors may be Ti-W (titanium-tungsten) adhesion layers and Ti (titanium) conductor layers.
  • Exemplary metal stacks useful as anode current collectors may be Ti-W adhesion layers, Au (gold) conductor layers, and In (indium) deposition layers.
  • the thickness of the PVD layers may be less than 500 nm in total.
  • the electrochemical and barrier properties may need to be compatible with the battery.
  • copper may be electroplated on top of a seed layer to grow a thick layer of conductor. Additional layers may be plated upon the copper.
  • copper may be electrochemically incompatible with certain electrolytes especially in the presence of zinc. Accordingly, if copper is used as a layer in the battery, it may need to be sufficiently isolated from the battery electrolyte. Alternatively, copper may be excluded or another metal substituted.
  • top and/or bottom packaging foils may also function as current collectors.
  • a 25 micron brass foil may be useful as an anode current collector for a zinc anode.
  • the brass foil may be optionally electroplated with indium prior to electroplating with zinc.
  • cathode current collector packaging foils may comprise titanium foil, Hastelloy C-276 foil, chromium foil, and/or tantalum foil.
  • one or more packaging foils may be fine blanked, embossed, etched, textured, laser machined, or otherwise processed to provide desirable form, surface roughness, and/or geometry to the final cell packaging.
  • a cathode mixture which may be a term for a chemical formulation used to form a battery's cathode, may be applied as a paste, gel, suspension, or slurry, and may comprise a transition metal oxide such as manganese dioxide, some form of conductive additive which, for example, may be a form of conductive powder such as carbon black or graphite, and a water-soluble polymer such as polyvinylpyrrolidone (PVP) or some other binder additive.
  • PVP polyvinylpyrrolidone
  • the cathode mixture may have a desirable rheology that allows it to either be dispensed onto desired portions of the separator and/or cathode current collector, or squeegeed through a screen or stencil in a similar manner.
  • the cathode mixture may be dried before being used in later cell assembly steps, while in other examples, the cathode may contain some or all of the electrolyte components, and may only be partially dried to a selected moisture content.
  • the transition metal oxide may, for example, be manganese dioxide.
  • the manganese dioxide which may be used in the cathode mixture may be, for example, electrolytic manganese dioxide (EMD) due to the beneficial additional specific energy that this type of manganese dioxide provides relative to other forms, such as natural manganese dioxide (NMD) or chemical manganese dioxide (CMD).
  • EMD electrolytic manganese dioxide
  • NMD natural manganese dioxide
  • CMD chemical manganese dioxide
  • the EMD useful in batteries of the present invention may need to have a particle size and particle size distribution that may be conducive to the formation of depositable or printable cathode mixture pastes/slurries.
  • the EMD may be processed to remove significant large particulate components that may be considered large relative to other features such as battery internal dimensions, separator thicknesses, dispense tip diameters, stencil opening sizes, or screen mesh sizes. Particle size optimization may also be used to improve performance of the battery, for example, internal impedance and discharge capacity.
  • Milling is the reduction of solid materials from one average particle size to a smaller average particle size, by crushing, grinding, cutting, vibrating, or other processes. Milling may also be used to free useful materials from matrix materials in which they may be embedded, and to concentrate minerals.
  • a mill is a device that breaks solid materials into smaller pieces by grinding, crushing, or cutting. There may be several means for milling and many types of materials processed in them. Such means of milling may include: ball mill, bead mill, mortar and pestle, roller press, and jet mill among other milling alternatives.
  • One example of milling that may be utilized in the present invention is jet milling. After the milling, the state of the solid is changed, for example, the particle size, the particle size disposition and the particle shape.
  • Aggregate milling processes may also be used to remove or separate contamination or moisture from aggregate to produce "dry fills" prior to transport or structural filling.
  • Some equipment may combine various techniques to sort a solid material into a mixture of particles whose size is bounded by both a minimum and maximum particle size. Such processing may be referred to as “classifiers” or “classification.”
  • Milling may be one aspect of cathode mixture production for uniform particle size distribution of the cathode mixture ingredients. Uniform particle size in a cathode mixture may assist in viscosity, rheology, electroconductivity, and other properties of a cathode. Milling may assist these properties by controlling agglomeration, or a mass collection, of the cathode mixture ingredients. Agglomeration - the clustering of disparate elements, which in the case of the cathode mixture, may be carbon allotropes and transition metal oxides - may negatively affect the filling process by leaving voids in the desired cathode cavity as illustrated in Fig. 11 and described subsequently.
  • filtration may be another important step for the removal of agglomerated or unwanted particles.
  • Unwanted particles may include over-sized particles, contaminates, or other particles not explicitly accounted for in the preparation process.
  • Filtration may be accomplished by means such as filter-paper filtration, vacuum filtration, chromatography, microfiltration, and other means of filtration.
  • EMD may have an average particle size of 7 microns with a large particle content that may contain particulates up to about 70 microns.
  • the EMD may be sieved, further milled, or otherwise separated or processed to limit large particulate content to below a certain threshold, for example, 25 microns or smaller.
  • the cathode may also comprise silver dioxide or nickel oxyhydroxide. Such materials may offer increased capacity and less decrease in loaded voltage during discharge relative to manganese dioxide, both desirable properties in a battery. Batteries based on these cathodes may have current examples present in industry and literature.
  • a novel microbattery utilizing a silver dioxide cathode may include a biocompatible electrolyte, for example, one comprising a zinc salt and/or an ammonium salt instead of potassium hydroxide.
  • Zinc/ammonium salts may include acetate, sulfate, bromide, gluconate, nitrate, and iodide.
  • the cathode mixture may include a polymeric binder.
  • the binder may serve a number of functions in the cathode mixture.
  • the primary function of the binder may be to create a sufficient inter-particle electrical network between EMD particles and carbon particles.
  • a secondary function of the binder may be to facilitate mechanical adhesion and electrical contact to the cathode current collector.
  • a third function of the binder may be to influence the rheological properties of the cathode mixture for advantageous dispensing and/or stenciling/screening.
  • a fourth function of the binder may be to enhance the electrolyte uptake and distribution within the cathode.
  • the choice of the binder polymer as well as the amount to be used may be beneficial to the function of the cathode in the electrochemical cell of the present invention. If the binder polymer is too soluble in the electrolyte to be used, then the primary function of the binder - electrical continuity - may be drastically impacted to the point of cell non-functionality. On the contrary, if the binder polymer is insoluble in the electrolyte to be used, portions of EMD may be ionically insulated from the electrolyte, resulting in diminished cell performance such as reduced capacity, lower open circuit voltage, and/or increased internal resistance.
  • the binder may be hydrophobic; it may also be hydrophilic.
  • binder polymers useful for the present invention comprise PVP, polyisobutylene (PIB), rubbery triblock copolymers comprising styrene end blocks such as those manufactured by Kraton Polymers, styrene-butadiene latex block copolymers, polyacrylic acid, hydroxyethylcellulose, carboxymethylcellulose, fluorocarbon solids such as polytetrafluoroethylene, among others.
  • a solvent may be one component of the cathode mixture.
  • a solvent may be useful in wetting the cathode mixture, which may assist in the particle distribution of the mixture.
  • a solvent may be toluene.
  • a surfactant may be useful in wetting, and thus distribution, of the cathode mixture.
  • a surfactant may be a detergent, such as Triton TM QS-44. Triton TM QS-44 may assist in the dissociation of aggregated ingredients in the cathode mixture, allowing for a more uniform distribution of the cathode mixture ingredients.
  • a conductive carbon may typically be used in the production of a cathode. Carbon is capable of forming many allotropes, or different structural modifications. Different carbon allotropes have different physical properties allowing for variation in electroconductivity. For example, the "springiness" of carbon black may help with adherence of a cathode mixture to a current collector. However, in energization elements requiring relatively low amounts of energy, these variations in electroconductivity may be less important than other favorable properties such as density, particle size, heat conductivity, and relative uniformity, among other properties.
  • carbon allotropes examples include: diamond, graphite, graphene, amorphous carbon (informally called carbon black), buckminsterfullerenes, glassy carbon (also called vitreous carbon), carbon aerogels, and other possible forms of carbon capable of conducting electricity.
  • a carbon allotrope may be graphite.
  • Table 1 Formulation Example Relative weight 80:20 JMEMD/KS6 4.900 PIB B10 (from 20percent solution) 0.100 toluene 2.980 Total 7.980 where PIB is polyisobutylene, JMEMD is jet milled manganese dioxide, KS6 is a graphite produced by Timcal, and PIB B10 is polyisobutylene with a molecular weight grade of B10.
  • the mixture may be dispensed, applied, and/or stored onto a surface such as the hydrogel separator, or the cathode current collector, or into a volume such as the cavity in the laminar structure. Filing onto a surface may result in a volume being filled over time.
  • a certain rheology may be desired to optimize the dispensing, applying, and/or storing process. For example, a less viscous rheology may allow for better filling of the cavity while at the same time possibly sacrificing particle distribution. A more viscous rheology may allow for optimized particle distribution, while possibly decreasing the ability to fill the cavity and possibly losing electroconductivity.
  • Figs. 10A-10F illustrate optimized and non-optimized dispensing or application into a cavity.
  • Fig. 10A illustrates a cavity optimally filled with the cathode mixture after application, dispensing, and/or storing.
  • Fig. 10B illustrates a cavity with insufficient filling in the bottom left quadrant 1002, which may be a direct result of undesirable cathode mixture rheology.
  • Fig. 10C illustrates a cavity with insufficient filling in the top right quadrant 1004, which may be a direct result of undesirable cathode mixture rheology.
  • Figs. 10A-10F illustrate optimized and non-optimized dispensing or application into a cavity.
  • Fig. 10A illustrates a cavity optimally filled with the cathode mixture after application, dispensing, and/or storing.
  • Fig. 10B illustrates a cavity with insufficient filling in the bottom left quadrant 1002, which may be a direct result of undesirable cathode mixture rhe
  • FIG. 10D and 10E illustrate a cavity with insufficient filling in the middle 1006 or bottom 1008 of the cavity, which may be a bubble caused by a direct result of undesirable cathode mixture rheology.
  • Fig. 10F illustrates a cavity with insufficient filling towards the top 1010 of the cavity, which may be a direct result of undesirable cathode mixture rheology.
  • the defects illustrated in Figs 10B-10F may result in several battery issues, for example, reduced capacity, increased internal resistance, and degraded reliability.
  • agglomeration 1102 may occur as a result of undesirable cathode mixture rheology. Agglomeration may result in decreased performance of the cathode mixture, for example, decreased discharge capacity and increased internal resistance.
  • the cathode mixture may resemble a peanut-butter like consistency optimized for squeegee filling the laminar construct cavity while maintaining electroconductivity.
  • the mixture may be viscous enough to be printed into the cavity.
  • the cathode mixture may be dried, placed, and stored in the cavity.
  • the anode for the laminar battery of the present invention may, for example, comprise zinc.
  • a zinc anode may take the physical form of a can in which the contents of the electrochemical cell may be contained.
  • a zinc can may be an example but there may be other physical forms of zinc that may prove desirable to realize ultra-small battery designs.
  • Electroplating of zinc is a process type in numerous industrial uses, for example, for the protective or aesthetic coating of metal parts.
  • electroplated zinc may be used to form thin and conformal anodes useful for batteries of the present invention.
  • the electroplated zinc may be patterned in many different configurations, depending on the design intent.
  • a facile means for patterning electroplated zinc may be processing with the use of a photomask or a physical mask.
  • a photoresist may be applied to a conductive substrate, the substrate on which zinc may subsequently be plated.
  • the desired plating pattern may be then projected to the photoresist by means of a photomask, thereby causing curing of selected areas of photoresist.
  • the uncured photoresist may then be removed with appropriate solvent and cleaning techniques.
  • the result may be a patterned area of conductive material that may receive an electroplated zinc treatment. While this method may provide benefit to the shape or design of the zinc to be plated, the approach may require use of available photopatternable materials, which may have constrained properties to the overall cell package construction. Consequently, new and novel methods for patterning zinc may be required to realize some designs of thin microbatteries of the present invention.
  • An alternative means of patterning zinc anodes may be by means of a physical mask application.
  • a physical mask may be made by cutting desirable apertures in a film having desirable barrier and/or packaging properties.
  • the film may have pressure-sensitive adhesive applied to one or both sides.
  • the film may have protective release liners applied to one or both adhesives. The release liner may serve the dual purpose of protecting the adhesive during aperture cutting and protecting the adhesive during specific processing steps of assembling the electrochemical cell, specifically the cathode filling step.
  • a zinc mask may comprise a PET film of approximately 100 microns thickness to which a pressure-sensitive adhesive may be applied to both sides in a layer thickness of approximately 10-20 microns.
  • Both PSA layers may be covered by a PET release film which may have a low surface energy surface treatment, and may have an approximate thickness of 50 microns.
  • the multi-layer zinc mask may comprise PSA and PET film.
  • PET films and PET/PSA zinc mask constructs as described herein may be desirably processed with precision nanosecond laser micromachining equipment, such as, an Oxford Lasers E-Series laser micromachining workstation, to create ultra-precise apertures in the mask to facilitate later plating.
  • nanosecond laser micromachining equipment such as, an Oxford Lasers E-Series laser micromachining workstation
  • the zinc mask may be placed and then electroplating of one or more metallic materials may be performed.
  • zinc may be electroplated directly onto an electrochemically compatible anode current collector foil such as brass.
  • anode side packaging comprises a polymer film or multi-layer polymer film upon which seed metallization has been applied
  • zinc, and/or the plating solutions used for depositing zinc may not be chemically compatible with the underlying seed metallization. Manifestations of lack of compatibility may include film cracking, corrosion, and/or exacerbated H 2 evolution upon contact with cell electrolyte. In such a case, additional metals may be applied to the seed metal to affect better overall chemical compatibility in the system.
  • One metal that may find particular utility in electrochemical cell constructions may be indium.
  • Indium may be widely used as an alloying agent in battery grade zinc with its primary function being to provide an anti-corrosion property to the zinc in the presence of electrolyte.
  • indium may be successfully deposited on various seed metallizations such as Ti-W and Au. Resulting films of 1-3 microns of indium on the seed metallization layers may be low-stress and adherent. In this manner, the anode-side packaging film and attached current collector having an indium top layer may be conformable and durable.
  • nodules of zinc may be observed to form on the underlying smooth indium deposit.
  • the vertical space allowance for the zinc anode layer may be up to about 5-10 microns thick, but in some examples, lower current densities may be used for zinc plating, and the resulting nodular growths may grow taller than the desired maximum anode vertical thickness. It may be that the nodular zinc growth stems from a combination of the high overpotential of indium and the presence of an oxide layer of indium.
  • higher current density DC plating may overcome the relatively large nodular growth patterns of zinc on indium surfaces.
  • 100 ASF plating conditions may result in nodular zinc, but the size of the zinc nodules may be drastically reduced compared to 20 ASF plating conditions.
  • the number of nodules may be vastly greater under 100 ASF plating conditions.
  • the resulting zinc film may ultimately coalesce to a more or less uniform layer with only some residual feature of nodular growth while meeting the vertical space allowance of about 5-10 microns.
  • An added benefit of indium in the electrochemical cell may be reduction of H 2 formation, which may be a slow process that occurs in aqueous electrochemical cells containing zinc.
  • the indium may be beneficially applied to one or more of the anode current collector, the anode itself as a co-plated alloying component, or as a surface coating on the electroplated zinc.
  • indium surface coatings may be desirably applied in-situ by way of an electrolyte additive such as indium trichloride or indium acetate. When such additives may be added to the electrolyte in small concentrations, indium may spontaneously plate on exposed zinc surfaces as well as portions of exposed anode current collector.
  • Zinc and similar anodes commonly used in commercial primary batteries may typically be found in sheet, rod, and paste forms.
  • the anode of a miniature, biocompatible battery may be of similar form, e.g. thin foil, or may be plated as previously mentioned.
  • the properties of this anode may differ significantly from those in existing batteries, for example, because of differences in contaminants or surface finish attributed to machining and plating processes. Accordingly, the electrodes and electrolyte may require special engineering to meet capacity, impedance, and shelf life requirements. For example, special plating process parameters, plating bath composition, surface treatment, and electrolyte composition may be needed to optimize electrode performance.
  • a battery has the following elements: cathode, anode, separator, electrolyte, cathode current collector, anode current collector, and packaging.
  • Clever design may try to combine these elements in easy to fabricate subassemblies.
  • optimized design may have dual-use components, such as, using a metal package to double as a current collector. From a relative volume and thickness standpoint, these elements may be nearly all the same volume, except for the cathode.
  • the electrochemical system may require about two (2) to ten (10) times the volume of cathode as anode due to significant differences in mechanical density, energy density, discharge efficiency, material purity, and the presence of binders, fillers, and conductive agents.
  • the packaging needed to provide sufficient protection to maintain battery chemistry in use environments may have a planned maximal thickness of approximately 50 ⁇ m.
  • such examples may assume a "pouch"-like construct, using webs or sheets fabricated into various configurations, with battery elements arranged inside.
  • the containment may have two films or one film folded over onto the other side either configuration of which may form two roughly planar surfaces, which may be then sealed on the perimeter to form a container.
  • This thin-but-wide form factor may make battery elements themselves thin and wide.
  • these examples may be suitable for application through coating, gravure printing, screen printing, sputtering, or other similar fabrication technology.
  • the internal components such as the anode, separator and cathode
  • these basic elements may be either "co-planar” that is side-by-side on the same plane or “co-facial” which may be face-to-face on opposite planes.
  • the anode, separator, and cathode may be deposited on the same surface.
  • the anode may be deposited on surface-1
  • the cathode may be deposited on surface-2
  • the separator may be placed between the two, either deposited on one of the sides, or inserted as its own separate element.
  • Another type of example may be classified as laminate assembly, which may involve using films, either in a web or sheet form, to build up a battery layer by layer.
  • Sheets may be bonded to each other using adhesives, such as pressure-sensitive adhesives, thermally activated adhesives, or chemical reaction-based adhesives.
  • the sheets may be bonded by welding techniques such as thermal welding, ultrasonic welding and the like.
  • Sheets may lend themselves to standard industry practices as roll-to-roll (R2R), or sheet-to-sheet assembly.
  • R2R roll-to-roll
  • an interior volume for cathode may need to be substantially larger than the other active elements in the battery.
  • Much of a battery construct may have to create the space of this cathode material, and support it from migration during flexing of the battery.
  • separator material Another portion of the battery construct that may consume significant portions of the thickness budget may be the separator material.
  • a sheet form of separator may create an advantageous solution for laminate processing.
  • the separator may be formed by dispensing hydrogel material into a layer to act as the separator.
  • the forming product may have an anode sheet, which may be a combination of a package layer and an anode current collector, as well as substrate for the anode layer.
  • the forming product may also have an optional separator spacer sheet, a cathode spacer sheet, and a cathode sheet.
  • the cathode sheet may be a combination of a package layer and a cathode current collector layer.
  • Intimate contact between electrodes and current collectors is of critical importance for reducing impedance and increasing discharge capacity. If portions of the electrode are not in contact with the current collector, resistance may increase since conductivity is then through the electrode (typically less conductive than the current collector) or a portion of the electrode may become totally disconnected. In coin cell and cylindrical batteries, intimacy is realized with mechanical force to crimp the can, pack paste into a can, or through similar means. Wave washers or similar springs are used in commercial cells to maintain force within the battery; however, these may add to the overall thickness of a miniature battery. In typical patch batteries, a separator may be saturated in electrolyte, placed across the electrodes, and pressed down by the external packaging.
  • the anode may be plated directly onto the current collector rather than using a paste. This process inherently results in a high level of intimacy and conductivity.
  • the cathode is typically a paste. Although binder material present in the cathode paste may provide adhesion and cohesion, mechanical pressure may be needed to ensure the cathode paste remains in contact with the cathode current collector. This may be especially important as the package is flexed and the battery ages and discharges, for example, as moisture leaves the package through thin and small seals.
  • Compression of the cathode may be achieved in the laminar, cofacial battery by introducing a compliant separator and/or electrolyte between the anode and cathode.
  • a gel electrolyte or hydrogel separator may compress on assembly and not simply run out of the battery as a liquid electrolyte might. Once the battery is sealed, the electrolyte and/or separator may then push back against the cathode.
  • An embossing step may be performed after assembly of the laminar stack, introducing compression into the stack.
  • the batteries according to the present invention may have important aspects relating to safety and biocompatibility.
  • batteries for biomedical devices may need to meet requirements above and beyond those for typical usage scenarios.
  • design aspects may be considered in relation to stressing events.
  • the safety of an electronic contact lens may need to be considered in the event a user breaks the lens during insertion or removal.
  • design aspects may consider the potential for a user to be struck in the eye by a foreign object.
  • stressful conditions that may be considered in developing design parameters and constraints may relate to the potential for a user to wear the lens in challenging environments like the environment under water or the environment at high altitude in non-limiting examples.
  • the safety of such a device may be influenced by: the materials that the device is formed with or from; the quantities of those materials employed in manufacturing the device; and the packaging applied to separate the devices from the surrounding on- or in-body environment.
  • pacemakers may be a typical type of biomedical device which may include a battery and which may be implanted in a user for an extended period of time.
  • pacemakers may typically be packaged with welded, hermetic titanium enclosures, or in other examples, multiple layers of encapsulation.
  • Emerging powered biomedical devices may present new challenges for packaging, especially battery packaging. These new devices may be much smaller than existing biomedical devices, for example, an electronic contact lens or pill camera may be significantly smaller than a pacemaker. In such examples, the volume and area available for packaging may be greatly reduced.
  • An advantage of the limited volume may be that amounts of materials and chemicals may be so small as to inherently limit the exposure potential to a user to a level below a safety limit.
  • the cavity-based laminate approach may provide means to enhance biocompatibility.
  • Each of the cavities may be surrounded by laminate material affording a relatively large sealing surface to battery volume ratio.
  • the volume of battery material that could leave the battery would be limited to that portion in a single cavity.
  • the batteries may be further sealed in additional encapsulation aspects, such as pockets of sealing materials, additional coatings of sealing materials, and different means of forming the various seals such as laser and thermal based sealing.
  • FIG. 12A a top-down view of an exemplary biocompatible energization element with encapsulation is illustrated.
  • An envelope capable of sealing 1201 may encapsulate the energization element containing at least an anode current collector 1202 with anode, a cathode current collector 1204 with cathode, and internal adhesives/sealants 1208.
  • the envelope capable of sealing 1201 may comprise polymer fills capable of sealing such as polypropylene.
  • the internal adhesives/sealants 1208 may comprise pressure-sensitive adhesives such as polyisobutylene.
  • Polyisobutylene is a commercially-available material that may be formulated into PSA compositions meeting many if not all requirements. Furthermore, PIB may be an excellent barrier sealant with very low water absorbance and low oxygen permeability.
  • An example of PIB useful in the examples of the present invention may be Oppanol® B15 by BASF Corporation.
  • Fig. 12B illustrates an exemplary bottom-up view of a biocompatible energization element with encapsulation.
  • Fig. 12B illustrates the capability of the plastic envelope capable of sealing 1201 to be sealed at different exemplary sealing sites 1206.
  • seals may be formed by a welding process that may involve thermal, laser, solvent, friction, ultrasonic, or arc processing.
  • seals may be formed through the use of adhesive sealants such as glues, epoxies, acrylics, natural rubber, and synthetic rubber.
  • Other examples may derive from the utilization of gasket type material that may be formed from cork, natural and synthetic rubber, polytetrafluoroethylene (PTFE), polypropylene, and silicones to mention a few non-limiting examples.
  • PTFE polytetrafluoroethylene
  • Fig. 12C illustrates an exemplary long-edge view of a biocompatible energization element with encapsulation containing an anode current collector 1202 with anode, a cathode current collector 1204 with cathode blend 1212, a separator 1210, adhesive/sealant 1208, and exemplary sealing sites 1206.
  • the envelope may enclose the components of the biocompatible energization element from the top and the bottom; however, the ends containing the anode current collector 1202 and cathode current collector 1204 may still be susceptible to leak.
  • sealing sites 1206 may become necessary.
  • the current collector sealing sites may be sealed by several sealing methods including, for example, the use welding, adhesives, lacquer, epoxy, aspalt, or heat treating the PSAs.
  • Well-designed sealing structures and the associated sealing materials may improve biocompatibility of the energization device as materials may be maintained in zones that have no interaction with biologically contacting surfaces.
  • well-formed seals may improve the ability of the battery to receive forces of various kinds and not rupture exposing the contents of the cavity or cavities of a battery.
  • the electrolyte composition and concentration may relate to the biocompatibility of the energization element.
  • lower concentrations than typically may be used for a given anode and cathode chemistry may result in improved biocompatibility while still maintaining good battery performance.
  • an electrolyte composition comprising roughly 20 percent ZnCl 2 may be common for zinc-based battery cells, a concentration of 10 percent or less may result in battery function that meets requirements while simultaneously improving the inherent biocompatibility of the battery device.
  • the electrolyte composition may be changed to other ionic species which may have improved biocompatibility.
  • packaging solution for a contact lens may be used as an electrolyte composition and have similar characteristics to tear fluid. This may result in improved operating characteristics for battery storage as well as improved biocompatibility.
  • the changes in electrolyte composition may be effected such that the electrolyte composition may resemble the composition of biofluids which may be proximate to the biomedical device. In the event of a breach, the egress of such electrolyte compositions may be expected to have a more favorable biocompatibility than other compositions.
  • the composition of the electrolyte may resemble tear fluid.
  • a battery may evolve gaseous species during the course of its use.
  • the choice of materials used to form the structure and encapsulation of the battery device may improve biocompatibility by allowing typical gasses evolved by operating battery conditions to diffuse outside the battery while otherwise retaining chemicals within the battery device.
  • a different type of example may relate to changing the nature of fluid chemicals within the battery device.
  • the electrolyte may be thickened by various thickening agents or by incorporation of the electrolyte into gelled materials. Thickened or gelled fluids will have greater difficulty in diffusing outside the battery device, which may improve the biocompatibility aspects of the device.
  • biocompatibility of the battery devices which have been formed according to the various manners described in the present invention.
  • these battery devices may be incorporated into biomedical devices such as ophthalmic lenses as discussed in reference to Fig 1B .
  • Biocompatibility of the biomedical device may be viewed both in terms of the direct impact of the battery devices as well as the consistency of the battery device to the biocompatibility of the biomedical device.
  • the battery device may be connected to an electroactive element where the battery resides within an insert with the electroactive element or outside the insert.
  • the insert, the electroactive element, and the battery as a whole may be encapsulated with appropriate hydrogel formulations to afford biocompatibility of the biomedical device.
  • the hydrogel may contain formulations that retain the wetting aspects of the encapsulating hydrogel.
  • the battery and the insert may interact with wetting aspects, and therefore the strategies for biocompatibility of the battery alone are very relevant to the overall biomedical device.
  • seals prevent ingress and egress of materials into the insert and into the battery device.
  • the design of the hydrogel encapsulating layer may be altered to allow wettability and permeability around the insert and the battery device, for example.
  • gas evolution may allow some gas species to pass through battery devices, through hydrogel encapsulation and into the biomedical device environment.
  • the portions of a biomedical device whether for an ophthalmic device or for other devices, that contact fluids and cell layers of a user may be designed for matching of the interface layers of the biomedical device to the biologic environment that the biomedical device will reside in or on.
  • the laminate processing described in the present invention may be used for some examples where the resulting battery devices are very small.
  • One metric of biocompatibility may relate to keeping the design of resulting battery devices to be very small, very thin, very flexible and the like. Therefore, the thin and small devices may present a more comfortable and therefore more biocompatible product when integrated into the biomedical device.
  • the thickness of the laminar structure formed with laminate processing and including the anode, cathode, separator, electrolytes, current collectors and laminate layers may be less than a millimeter across at least one dimension.
  • the thickness of the laminar structure with all these components may be less than 500 microns across at least one dimension. In still further examples, the thickness of the laminar structure with all these components may be less than 250 microns.
  • a preferred encapsulating material that may form an encapsulating layer in a biomedical device may include a silicone containing component.
  • this encapsulating layer may form a lens skirt of a contact lens.
  • a "silicone-containing component" is one that contains at least one [-Si-O-] unit in a monomer, macromer or prepolymer.
  • the total Si and attached O are present in the silicone-containing component in an amount greater than about 20 weight percent, and more preferably greater than 30 weight percent of the total molecular weight of the silicone-containing component.
  • Useful silicone-containing components preferably comprise polymerizable functional groups such as acrylate, methacrylate, acrylamide, methacrylamide, vinyl, N-vinyl lactam, N-vinylamide, and styryl functional groups.
  • the ophthalmic lens skirt also called an insert-encapsulating layer, that surrounds the insert may be comprised of standard hydrogel ophthalmic lens formulations.
  • Exemplary materials with characteristics that may provide an acceptable match to numerous insert materials may include, the Narafilcon family (including Narafilcon A and Narafilcon B), and the Etafilcon family (including Etafilcon A).
  • Narafilcon family including Narafilcon A and Narafilcon B
  • Etafilcon family including Etafilcon A
  • Suitable silicone containing components include compounds of Formula I where
  • “monovalent reactive groups” are groups that may undergo free radical and/or cationic polymerization.
  • free radical reactive groups include (meth)acrylates, styryls, vinyls, vinyl ethers, C1-6alkyl(meth)acrylates, (meth)acrylamides, C1-6alkyl(meth)acrylamides, N-vinyllactams, N-vinylamides, C2-12alkenyls, C2-12alkenylphenyls, C2-12alkenylnaphthyls, C2-6alkenylphenylC1-6alkyls, O-vinylcarbamates and O-vinylcarbonates.
  • Non-limiting examples of cationic reactive groups include vinyl ethers or epoxide groups and mixtures thereof.
  • the free radical reactive groups comprises (meth)acrylate, acryloxy, (meth)acrylamide, and mixtures thereof.
  • Suitable monovalent alkyl and aryl groups include unsubstituted monovalent C1 to C16alkyl groups, C6-C14 aryl groups, such as substituted and unsubstituted methyl, ethyl, propyl, butyl, 2-hydroxypropyl, propoxypropyl, polyethyleneoxypropyl, combinations thereof and the like.
  • b is zero, one R1 is a monovalent reactive group, and at least 3 R1 are selected from monovalent alkyl groups having one to 16 carbon atoms, and in another example from monovalent alkyl groups having one to 6 carbon atoms.
  • Non-limiting examples of silicone components of this embodiment include 2-methyl-,2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester ("SiGMA”), 2-hydroxy-3-methacryloxypropyloxypropyl-tris (trimethylsiloxy)silane, 3-methacryloxypropyltris(trimethylsiloxy)silane (“TRIS”), 3-methacryloxypropylbis(trimethylsiloxy)methylsilane and 3-methacryloxypropylpentamethyl disiloxane.
  • SiGMA 2-methyl-,2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester
  • TMS 3-methacryloxypropyltris(trimethylsiloxy)silane
  • TMS 3-methacryloxypropylbis(trimethylsil
  • b is 2 to 20, 3 to 15 or in some examples 3 to 10; at least one terminal R1 comprises a monovalent reactive group and the remaining R1 are selected from monovalent alkyl groups having 1 to 16 carbon atoms, and in another embodiment from monovalent alkyl groups having 1 to 6 carbon atoms.
  • b is 3 to 15, one terminal R1 comprises a monovalent reactive group, the other terminal R1 comprises a monovalent alkyl group having 1 to 6 carbon atoms and the remaining R1 comprise monovalent alkyl group having 1 to 3 carbon atoms.
  • Non-limiting examples of silicone components of this embodiment include (mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated polydimethylsiloxane (400-1000 MW)) (“OH-mPDMS”), monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxanes (800-1000 MW), (“mPDMS”).
  • both terminal R1 comprise monovalent reactive groups and the remaining R1 are independently selected from monovalent alkyl groups having 1 to 18 carbon atoms, which may have ether linkages between carbon atoms and may further comprise halogen.
  • the lens of the present invention will be made from a reactive mixture comprising at least about 20 and preferably between about 20 and 70%wt silicone containing components based on total weight of reactive monomer components from which the polymer is made.
  • one to four R1 comprises a vinyl carbonate or carbamate of the formula: wherein:
  • the silicone-containing vinyl carbonate or vinyl carbamate monomers specifically include: 1,3-bis[4-(vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane; 3-(vinyloxycarbonylthio) propyl-[tris (trimethylsiloxy)silane]; 3-[tris(trimethylsiloxy)silyl] propyl allyl carbamate; 3-[tris(trimethylsiloxy)silyl] propyl vinyl carbamate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate, and
  • R1 shall comprise a monovalent reactive group and no more than two of the remaining R1 groups will comprise monovalent siloxane groups.
  • silicone-containing components includes polyurethane macromers of the following formulae:
  • a preferred silicone-containing component is a polyurethane macromer represented by formula IX wherein R16 is a diradical of a diisocyanate after removal of the isocyanate group, such as the diradical of isophorone diisocyanate.
  • Another suitable silicone containing macromer is compound of formula X (in which x + y is a number in the range of 10 to 30) formed by the reaction of fluoroether, hydroxy-terminated polydimethylsiloxane, isophorone diisocyanate and isocyanatoethylmethacrylate.
  • silicone-containing components suitable for use in this invention include macromers containing polysiloxane, polyalkylene ether, diisocyanate, polyfluorinated hydrocarbon, polyfluorinated ether and polysaccharide groups; polysiloxanes with a polar fluorinated graft or side group having a hydrogen atom attached to a terminal difluoro-substituted carbon atom; hydrophilic siloxanyl methacrylates containing ether and siloxanyl linkanges and crosslinkable monomers containing polyether and polysiloxanyl groups.
  • the polymer backbone may have zwitterions incorporated into it.
  • zwitterions may exhibit charges of both polarity along the polymer chain when the material is in the presence of a solvent.
  • the presence of the zwitterions may improve wettability of the polymerized material.
  • any of the foregoing polysiloxanes may also be used as an encapsulating layer in the present invention.
  • the biocompatible batteries may be used in biocompatible devices such as, for example, implantable electronic devices, such as pacemakers and micro-energy harvesters, electronic pills for monitoring and/or testing a biological function, surgical devices with active components, ophthalmic devices, microsized pumps, defibrillators, stents, and the like.
  • implantable electronic devices such as pacemakers and micro-energy harvesters
  • electronic pills for monitoring and/or testing a biological function
  • surgical devices with active components such as, ophthalmic devices, microsized pumps, defibrillators, stents, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Biomedical Technology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cardiology (AREA)
  • Power Engineering (AREA)
  • Primary Cells (AREA)
  • Battery Mounting, Suspending (AREA)
  • Eyeglasses (AREA)
  • Materials For Medical Uses (AREA)
EP15181799.6A 2014-08-21 2015-08-20 Biocompatibilité des éléments énergétiques biomédicaux Withdrawn EP2996172A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462040178P 2014-08-21 2014-08-21
US14/827,589 US9923177B2 (en) 2014-08-21 2015-08-17 Biocompatibility of biomedical energization elements

Publications (2)

Publication Number Publication Date
EP2996172A2 true EP2996172A2 (fr) 2016-03-16
EP2996172A3 EP2996172A3 (fr) 2016-07-13

Family

ID=53938207

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15181799.6A Withdrawn EP2996172A3 (fr) 2014-08-21 2015-08-20 Biocompatibilité des éléments énergétiques biomédicaux

Country Status (12)

Country Link
US (2) US9923177B2 (fr)
EP (1) EP2996172A3 (fr)
JP (1) JP2016045499A (fr)
KR (1) KR101895560B1 (fr)
CN (1) CN105390708A (fr)
AU (1) AU2015215936A1 (fr)
BR (1) BR102015020087A2 (fr)
CA (1) CA2900872A1 (fr)
HK (1) HK1221558A1 (fr)
RU (1) RU2675591C2 (fr)
SG (1) SG10201506618SA (fr)
TW (1) TWI656679B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170200923A1 (en) * 2014-07-21 2017-07-13 Johnson & Johnson Vision Care, Inc. Flexible micro-battery
EP3392925A1 (fr) * 2017-04-19 2018-10-24 Johnson & Johnson Vision Care Inc. Microbatterie souple
RU2683593C1 (ru) * 2017-04-19 2019-03-29 Джонсон Энд Джонсон Вижн Кэа, Инк. Гибкая микробатарея

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3486992B1 (fr) 2013-06-28 2020-09-23 Positec Power Tools (Suzhou) Co., Ltd Batterie
US20200119316A9 (en) * 2014-07-21 2020-04-16 Johnson & Johnson Vision Care, Inc. Flexible micro-battery
US10879503B2 (en) * 2014-07-21 2020-12-29 Johnson & Johnson Vision Care, Inc. Methods for the manufacture of flexible microbatteries
US11069891B2 (en) * 2014-09-26 2021-07-20 Positec Power Tools (Suzhou) Co., Ltd. Battery, battery pack and continuous power supply
US9857608B2 (en) 2015-03-20 2018-01-02 Quantum Medical Innovations Llc Point-of-use-activated microbattery and biocompatible electronic device incorporating the same
US11362382B2 (en) 2016-05-09 2022-06-14 International Business Machines Corporation Simplified hermetic packaging of a micro-battery
BR102017019397A2 (pt) * 2016-09-12 2018-05-02 Johnson & Johnson Vision Care, Inc. Baterias em formato tubular para um dispositivo biomédico
US10734668B2 (en) 2016-09-12 2020-08-04 Johnson & Johnson Vision Care, Inc. Tubular form biomedical device batteries
US20180076465A1 (en) * 2016-09-12 2018-03-15 Johnson & Johnson Vision Care, Inc. Tubular form biomedical device batteries with electroless sealing
US20180104921A1 (en) * 2016-10-17 2018-04-19 Johnson & Johnson Vision Care, Inc. Biomedical device batteries with electrodeposited cathodes
KR101891668B1 (ko) 2017-07-27 2018-08-24 한국과학기술연구원 전고상 박막 이차 전지가 장착된 스마트 웨어러블 렌즈 및 그 제조 방법
KR102036535B1 (ko) * 2017-11-28 2019-11-26 (주)뉴옵틱스 체내 이식형 의료기기
US20220004026A1 (en) * 2020-07-02 2022-01-06 Purdue Research Foundation Contact lens having sensors and methods for producing the same

Family Cites Families (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2007518A1 (de) 1969-02-20 1971-02-04 Union Carbide Corp , New York,N Y (V St A) Elektrolyt fur Pnmarzellen
JPS485185B1 (fr) 1969-05-16 1973-02-14
US4125686A (en) 1977-06-30 1978-11-14 Polaroid Corporation Laminar cells and methods for making the same
US4977046A (en) 1982-04-26 1990-12-11 Polaroid Corporation Lithium batteries
US5300371A (en) * 1990-03-23 1994-04-05 Battery Technologies Inc. Manganese dioxide positive electrode for rechargeable cells, and cells containing the same
US5358539A (en) 1992-10-29 1994-10-25 Valence Technology, Inc. Method for making a battery assembly
US5418091A (en) 1993-03-05 1995-05-23 Bell Communications Research, Inc. Polymeric electrolytic cell separator membrane
US5540741A (en) 1993-03-05 1996-07-30 Bell Communications Research, Inc. Lithium secondary battery extraction method
WO1994023334A1 (fr) 1993-04-07 1994-10-13 The Technology Partnership Plc Lentille commutable
WO1997017737A1 (fr) 1995-11-06 1997-05-15 Battery Technologies Inc. Piles alcalines rechargeables contenant des anodes en zinc non additionnees de mercure
US6933331B2 (en) 1998-05-22 2005-08-23 Nanoproducts Corporation Nanotechnology for drug delivery, contrast agents and biomedical implants
ID26512A (id) * 1998-05-05 2001-01-11 Bausch & Lomb Perlakuan permukaan plasma pada lensa kontak silikon hidrogel
WO2000004601A1 (fr) 1998-07-16 2000-01-27 Koninklijke Philips Electronics N.V. Pile secondaire au lithium
US6379835B1 (en) 1999-01-12 2002-04-30 Morgan Adhesives Company Method of making a thin film battery
US6273904B1 (en) 1999-03-02 2001-08-14 Light Sciences Corporation Polymer battery for internal light device
US6277520B1 (en) 1999-03-19 2001-08-21 Ntk Powerdex, Inc. Thin lithium battery with slurry cathode
US6316142B1 (en) 1999-03-31 2001-11-13 Imra America, Inc. Electrode containing a polymeric binder material, method of formation thereof and electrochemical cell
US6391069B1 (en) 2000-03-29 2002-05-21 Valence Technology (Nevada), Inc. Method of making bonded-electrode rechargeable electrochemical cells
JP5103693B2 (ja) * 2000-09-19 2012-12-19 大日本印刷株式会社 電池用積層フィルムおよびそれを用いた電池用容器
US6781817B2 (en) 2000-10-02 2004-08-24 Biosource, Inc. Fringe-field capacitor electrode for electrochemical device
US6727022B2 (en) 2001-11-19 2004-04-27 Wilson Greatbatch Ltd. Powder process for double current collector screen cathode preparation
US6780347B2 (en) 2002-02-04 2004-08-24 Rayovac Corporation Manganese oxide based electrode for alkaline electrochemical system and method of its production
JP5021889B2 (ja) 2002-02-12 2012-09-12 エバレデイ バツテリ カンパニー インコーポレーテツド 可撓性の薄い印刷電池およびデバイス並びにその製造方法
CA2389907A1 (fr) 2002-06-07 2003-12-07 Battery Technologies Inc. Cellule electrochimique rechargeable de petit format, a haute densite de courant et a plaques planes
US20040062985A1 (en) 2002-09-30 2004-04-01 Aamodt Paul B. Contoured battery for implantable medical devices and method of manufacture
US7205072B2 (en) 2002-11-01 2007-04-17 The University Of Chicago Layered cathode materials for lithium ion rechargeable batteries
US8076031B1 (en) 2003-09-10 2011-12-13 West Robert C Electrochemical device having electrolyte including disiloxane
WO2004095606A2 (fr) 2003-04-23 2004-11-04 Rechargeable Battery Corporation Accumulateur utilisant un batonnet electrode qui contient une electrode interieure incorporee
JP4598001B2 (ja) 2003-12-30 2010-12-15 エルジー・ケム・リミテッド イオン性液体によって改質された正極及びこれを含む電気化学素子
US7531271B2 (en) 2004-03-18 2009-05-12 The Gillette Company Wafer alkaline cell
US20060099496A1 (en) 2004-10-29 2006-05-11 Aamodt Paul B Separator container
US20070125644A1 (en) 2005-09-15 2007-06-07 Board Of Regents, The University Of Texas System Reduction of the loss of zinc by its reaction with oxygen in galvanized steel and batteries
CN101351907B (zh) 2005-10-11 2010-09-29 埃克塞勒特龙固体公司 制造锂电池的方法
WO2007070717A2 (fr) 2005-12-15 2007-06-21 Cardiac Pacemakers, Inc. Procede et dispositif pour batterie souple destinee a un dispositif implantable
US20070141463A1 (en) 2005-12-21 2007-06-21 Maya Stevanovic Cathode for battery
JP2008078119A (ja) 2006-08-25 2008-04-03 Ngk Insulators Ltd 全固体蓄電素子
EP2176814A4 (fr) 2007-07-18 2012-06-13 Blue Spark Technologies Inc Dispositif électronique intégré et ses procédés de préparation
WO2009018315A2 (fr) 2007-08-01 2009-02-05 Blue Spark Technologies, Inc. Dispositif électronique intégré et procédés de fabrication de celui-ci
US20090092903A1 (en) 2007-08-29 2009-04-09 Johnson Lonnie G Low Cost Solid State Rechargeable Battery and Method of Manufacturing Same
KR20100097217A (ko) 2007-12-19 2010-09-02 블루 스파크 테크놀러지스, 인크. 고전류의 박형 전기화학적 셀 및 이의 제조 방법
JP4484936B2 (ja) 2008-05-13 2010-06-16 シャープ株式会社 燃料電池および燃料電池スタック
RU78007U1 (ru) * 2008-07-04 2008-11-10 Открытое акционерное общество "Энергия" Марганцево-цинковый химический источник тока с солевым электролитом и батарея на его основе
US9675443B2 (en) 2009-09-10 2017-06-13 Johnson & Johnson Vision Care, Inc. Energized ophthalmic lens including stacked integrated components
US9296158B2 (en) * 2008-09-22 2016-03-29 Johnson & Johnson Vision Care, Inc. Binder of energized components in an ophthalmic lens
US20100078837A1 (en) 2008-09-29 2010-04-01 Pugh Randall B Apparatus and method for formation of an energized ophthalmic device
US9375885B2 (en) * 2008-10-31 2016-06-28 Johnson & Johnson Vision Care, Inc. Processor controlled ophthalmic device
LT2459220T (lt) * 2009-07-31 2020-12-28 Ascendis Pharma A/S Biologiškai suyrantys vandenyje netirpūs hidrogeliai polietilenglikolio pagrindu
GB0913722D0 (en) 2009-08-06 2009-09-16 Bac2 Ltd Electrical device
US8697770B2 (en) * 2010-04-13 2014-04-15 Johnson & Johnson Vision Care, Inc. Pupil-only photochromic contact lenses displaying desirable optics and comfort
CN102959769A (zh) 2010-04-28 2013-03-06 弗莱克赛尔有限责任公司 薄的柔性电化学能量电池
JP2012099470A (ja) 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd リチウム二次電池用正極材料前駆体の製造方法およびリチウム二次電池用正極材料の製造方法
US9698129B2 (en) 2011-03-18 2017-07-04 Johnson & Johnson Vision Care, Inc. Stacked integrated component devices with energization
US20120282519A1 (en) * 2011-05-06 2012-11-08 Greatbatch Ltd. Dissimilar Material Battery Enclosure for Improved Weld Structure
EP2631962B1 (fr) * 2011-08-29 2017-04-26 Panasonic Intellectual Property Management Co., Ltd. Batterie mince
AU2012352003B2 (en) 2011-12-14 2015-10-01 Arrow International, Inc. Redox processes for contact lens modification
WO2013090780A1 (fr) * 2011-12-14 2013-06-20 Semprus Biosciences Corp. Lentilles de contact à surface modifiée
SG11201404172TA (en) * 2012-01-26 2014-10-30 Johnson & Johnson Vision Care Energized ophthalmic lens including stacked integrated components
US9059435B2 (en) 2012-01-27 2015-06-16 Medtronic, Inc. Medical device battery enclosure
GB201203713D0 (en) 2012-03-02 2012-04-18 Energy Diagnostic Ltd Energy storage battery
US9178200B2 (en) 2012-05-18 2015-11-03 24M Technologies, Inc. Electrochemical cells and methods of manufacturing the same
US20140000101A1 (en) * 2012-06-29 2014-01-02 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form printed batteries on ophthalmic devices
KR101759806B1 (ko) 2012-11-01 2017-07-19 블루 스파크 테크놀러지스, 인크. 체온 기록 패치
US20150228986A1 (en) 2012-11-07 2015-08-13 James Y. Wang Liquid-activated hydrogel battery
US10033029B2 (en) 2012-11-27 2018-07-24 Apple Inc. Battery with increased energy density and method of manufacturing the same
US9406969B2 (en) 2013-03-15 2016-08-02 Johnson & Johnson Vision Care, Inc. Methods and apparatus to form three-dimensional biocompatible energization elements
WO2014169218A2 (fr) * 2013-04-12 2014-10-16 The Board Of Trustees Of The University Of Illinois Matériaux, systèmes électroniques et modes pour effet transitoire actif et passif
CN203300756U (zh) * 2013-06-07 2013-11-20 广东国光电子有限公司 一种软包装聚合物锂离子电池手工封装装置
US9455423B2 (en) 2014-01-24 2016-09-27 Verily Life Sciences Llc Battery
US9806299B2 (en) 2014-04-08 2017-10-31 International Business Machines Corporation Cathode for thin film microbattery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170200923A1 (en) * 2014-07-21 2017-07-13 Johnson & Johnson Vision Care, Inc. Flexible micro-battery
US10593911B2 (en) * 2014-07-21 2020-03-17 Johnson & Johnson Vision Care, Inc. Flexible micro-battery
EP3392925A1 (fr) * 2017-04-19 2018-10-24 Johnson & Johnson Vision Care Inc. Microbatterie souple
RU2682724C1 (ru) * 2017-04-19 2019-03-21 Джонсон Энд Джонсон Вижн Кэа, Инк. Гибкая микробатарея
RU2683593C1 (ru) * 2017-04-19 2019-03-29 Джонсон Энд Джонсон Вижн Кэа, Инк. Гибкая микробатарея

Also Published As

Publication number Publication date
RU2015135169A3 (fr) 2018-06-19
HK1221558A1 (zh) 2017-06-02
KR101895560B1 (ko) 2018-09-07
EP2996172A3 (fr) 2016-07-13
RU2675591C2 (ru) 2018-12-20
CA2900872A1 (fr) 2016-02-21
CN105390708A (zh) 2016-03-09
RU2015135169A (ru) 2017-02-27
BR102015020087A2 (pt) 2016-02-23
US20160056417A1 (en) 2016-02-25
US9923177B2 (en) 2018-03-20
SG10201506618SA (en) 2016-03-30
US20180159091A1 (en) 2018-06-07
KR20160023614A (ko) 2016-03-03
TW201620194A (zh) 2016-06-01
TWI656679B (zh) 2019-04-11
AU2015215936A1 (en) 2016-03-10
JP2016045499A (ja) 2016-04-04

Similar Documents

Publication Publication Date Title
US9923177B2 (en) Biocompatibility of biomedical energization elements
US10598958B2 (en) Device and methods for sealing and encapsulation for biocompatible energization elements
US9946092B2 (en) Methods for manufacturing biocompatible cathode slurry for use in biocompatible batteries
US20170229730A1 (en) Method for manufacturing a biocompatible cathode slurry for use in biocompatible batteries for a contact lens
EP2996187B1 (fr) Mélange pour cathode à utiliser dans une batterie biocompatible
EP2996182B1 (fr) Formulations d'électrolyte pour utilisation dans des éléments énergétiques biocompatibles
US10367233B2 (en) Biomedical energization elements with polymer electrolytes and cavity structures
EP3396742A1 (fr) Procédé de fabrication d'une suspension cathodique biocompatible à utiliser dans des batteries biocompatibles pour une lentille de contact
EP3312911A1 (fr) Éléments biomédicaux d'énergisation avec des électrolytes polymères
US10361404B2 (en) Anodes for use in biocompatible energization elements
EP3174129A1 (fr) Éléments d'excitation biomédicale avec électrolytes polymères et structures en cavités

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: B29D 11/00 20060101ALN20160223BHEP

Ipc: G02C 7/08 20060101ALN20160223BHEP

Ipc: H01M 2/02 20060101AFI20160223BHEP

Ipc: H01M 10/26 20060101ALI20160223BHEP

Ipc: H01M 10/04 20060101ALN20160223BHEP

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: B29D 11/00 20060101ALN20160608BHEP

Ipc: H01M 10/26 20060101ALI20160608BHEP

Ipc: H01M 2/02 20060101AFI20160608BHEP

Ipc: H01M 10/04 20060101ALN20160608BHEP

Ipc: G02C 7/04 20060101ALI20160608BHEP

17P Request for examination filed

Effective date: 20170113

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1221558

Country of ref document: HK

R17P Request for examination filed (corrected)

Effective date: 20170113

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20200303

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1221558

Country of ref document: HK